TW202028317A - Resin film and method for manufacturing same - Google Patents

Abstract

Provided is a resin film for which the manufacturing load can be reduced by decreasing the number of steps in the manufacturing process, the resin film having both antistatic properties and scratch resistance, wherein the antistatic properties do not tend to change due to the environment (i.e., have excellent stability). In this resin film, at least one surface has an insulator phase (A) and a conductor phase (B) that are measured by conductive AFM, and when the surface having the insulator phase (A) and the conductor phase (B) is surface [alpha], the area occupied by the insulator phase (A) on the surface [alpha] is 40-80%, and the surface resistivity of the surface [alpha] is 1010 [Omega]/□ or less.

Description

Resin film and its manufacturing method

The present invention relates to a resin film and its manufacturing method.

Thermoplastic resin films, especially biaxially oriented polyester films, have excellent properties such as mechanical properties, electrical properties, dimensional stability, transparency, and chemical resistance, so they are widely used in various applications such as magnetic recording materials and packaging materials. . Especially in recent years, in addition to carrier films for various industrial product processing steps, it is also aimed at displays such as touch panels, liquid crystal display panels (LCD), plasma display panels (PDP), organic electroluminescence (organic EL), etc. Various optical films for component applications, etc., require higher quality of polyester films. In this context, for the purpose of suppressing scratches and foreign matter in the production and processing steps of the polyester film, it is required to have both "antistatic properties" and "scratch resistance".

The antistatic property is a characteristic given for the purpose of suppressing the adhesion of dust caused by static electricity and causing defects of foreign matter. For example, Patent Document 1 describes a method of adding antistatic to a polyester resin and coating, and Patent Document 2 describes a method of coating a styrene sulfonic acid copolymer. Practical issues often cause changes in the antistatic properties due to environmental changes such as humidity, temperature, and elapsed time from the start of manufacture, and occasionally cause problems.

On the other hand, the scratch resistance is a characteristic given for the purpose of suppressing the surface being cut due to contact and slippage of the conveying roller during processing. For example The layer is a hard-coated film made of ultraviolet (UV) curable resin (hard coat layer), but when cutting, punching, etc., the scratch-resistant layer is required to be beautifully punched without cracks (cracks) Processability. If the workability is poor, cracks will occur at the end, which will impair the design, or breakage and other related defects.

In response to these requirements, Patent Document 3 proposes a film in which a conductive material is mixed with a hard coat layer, and Patent Document 4 proposes a laminate film in which a hard coat layer is further coated on the antistatic layer.

[Prior Technical Literature] [Patent Literature]

Patent Document 1: Japanese Patent Laid-Open No. 61-204240

Patent Document 2: Japanese Patent Laid-open No. 7-10016

Patent Document 3: Japanese Patent Laid-Open No. 2011-033658

Patent Document 4: Japanese Patent Laid-Open No. 2008-176317

However, for example, in Patent Documents 1 and 2, the laminated film provided with an antistatic layer has an insufficient effect of suppressing scratches during the processing step. On the other hand, according to the technical system described in Patent Documents 3 and 4, scratches can be suppressed. However, Patent Document 3 cannot sufficiently balance scratch resistance and antistatic properties. In addition, the technology of Patent Document 4 has insufficient antistatic performance in the step after the hard coating process.

The reason is that, in order to solve the above-mentioned shortcomings, the subject of the present invention is to provide a technology for mass-production of resin films that can achieve both antistatic properties and scratch resistance.

In order to solve the aforementioned problems, the resin film of the present invention has the following configuration.

(1) A resin film in which at least one surface is provided with a conductivity measurement mode (conductive AFM) using AFM (Atomic Force Microscope), and the measured insulating phase (A) and conductive phase (B), When the surface provided with the insulating phase (A) and the conductive phase (B) is set as the surface α, the area occupied by the insulating phase (A) in the surface α is 40% or more and 80% or less, and the surface of the surface α The resistivity is 10 ¹⁰ Ω/□ or less.

(2) The resin film according to (1), wherein the average area diameter of the insulating phase (A) in the surface α is 50 nm or more and 200 nm or less.

(3) (1) or (2) a resin film described above, wherein the surface α of the insulating phase (A) electrically conductive I _A, the ratio of the conductive phase (B) conductive I _B of I _A /I _B is above 100 and below 100,000.

(4) The resin film according to any one of (1) to (3), wherein the haze change of the surface α before and after the wiping treatment is 3.0% or less.

(5) The resin film according to any one of (1) to (4), wherein in the surface α, the elastic modulus (GA) of the insulating phase ( _A ) is 2000 MPa or more and 50000 MPa or less.

The elastic (6) (1) to (5) in the resin film according to any one of claims, wherein the α surface, the insulating phase (A) elastic modulus (G _A), the conductive phase (B) of The ratio of modulus (G _B ) G _A /G _B is 4 or more and 20 or less.

(7) The resin film according to any one of (1) to (6), which contains a laminate of two or more layers including a supporting base material and a layer (X) formed on the surface thereof.

(8) The resin film according to any one of (1) to (7), wherein the insulating phase (A) contains metal oxide particles (a), and the metal oxide particles (a) contain At least one metal element is selected from the group consisting of Si, Al, Ti, Zr, Se, and Fe.

唑啉化合物、羰二醯亞胺化合物、異氰酸酯化合物中選擇至少1種交聯劑(c)。 (9) The resin film according to any one of (1) to (8), wherein the conductive phase (B) contains: a polythiophene-based conductive compound (b), and epoxy resin, melamine resin ,

At least one crosslinking agent (c) is selected from the oxazoline compound, carbonyldiimide compound, and isocyanate compound.

唑啉化合物、羰二醯亞胺化合物、異氰酸酯化合物中選擇至少1種交聯劑(c)。 (10) A method for manufacturing a resin film, which is the method for manufacturing a resin film as described in any one of (1) to (9), including: coating a paint on at least one side of the polyester film before crystallization is completed After the composition (x), the steps of stretching treatment and heat treatment are performed in at least one direction; and the coating composition (x) contains: metal oxide particles (a), conductive components (b), and epoxy resin Resin, melamine resin,

At least one crosslinking agent (c) is selected from the oxazoline compound, carbonyldiimide compound, and isocyanate compound.

The resin film of the present invention has antistatic properties and scratch resistance combined, and has less changes in the antistatic environment (that is, excellent stability). By shortening the number of manufacturing steps, the manufacturing load can be reduced.

Fig. 1 is a schematic diagram of the conductivity distribution obtained by measuring the surface of the resin film of the present invention using the AFM (Atomic Force Microscope) conductivity measurement mode (conductive AFM). (In the actual measurement, the 1μm×1μm conductive image is divided into 40 vertical and horizontal directions, and divided into 1600 25nm×25nm regions, but the schematic diagram is that the 1μm×1μm conductive image is divided into 20 vertical and horizontal directions.)

Hereinafter, the resin film of the present invention will be described in detail. The resin film of the present invention is provided with a conductivity measurement mode (conductive AFM) by AFM (Atomic Force Microscope) on at least one surface, and the measured insulating phase (A) and conductive phase (B) are When the surface provided with the insulating phase (A) and the conductive phase (B) is set as the surface α, the area occupied by the insulating phase (A) in the surface α must be 40% or more and 80% or less, and the surface of the laminated film The resistivity must be below 1×10 ¹⁰ Ω/□.

First, FIG. 1 shows a schematic diagram of the conductivity distribution measured by the conductive AFM on the surface of the resin film of the present invention. As shown in Fig. 1, the resin film of the present invention must be provided with two regions with different physical properties on at least one surface. Specifically, when using the conductive AFM method to measure the surface, there must be an area with relatively high conductivity (hereinafter referred to as "conductive phase (B)") and an area with relatively low conductivity (hereinafter referred to as "insulating phase (A)" )”). As will be described in detail later, the image obtained by the conductive AFM measurement is binarized using "ScionImage" [Maximum: 10nA, Minimum: 0pA, Threshold 180 (Set black to 0, white to 255, from black to In the gray scale represented by white in 256 steps, the area flowing 10nA or more becomes 255 (white), and the area of 0pA becomes 0 (black). The conductive image is made. In the obtained conductive image, the gray scale The higher part of the current value represented by the color of 180 or more is represented in white, and the lower part of the current value represented by the gray scale of less than 180 is represented by black.)], and the conductive image is obtained. The obtained conductive image 1μm×1μm is divided into 40 vertical and horizontal sections, and divided into 1600 25nm×25nm regions. Among the 1600 regions, one region with pure black is set as the insulating phase (A), all of which are The pure white is set as the conductive phase (B). In order to solve the problem of the present invention, the inventors conducted in-depth studies and confirmed that the materials used for imparting antistatic properties are mostly composed of low-hardness polymers or aggregates of low-molecular-weight materials, and their properties are easily affected by pressure and temperature. , Humidity and other external stimuli appear to change. However, in response to this phenomenon, it was found that the provision of the film on the surface of the film is essentially free of antistatic components The insulating phase (A) of the area can balance antistatic and scratch resistance, and can achieve antistatic stability.

In addition, the insulating phase (A) of the surface α must have a necessary ratio in the entire area of the surface α. Specifically, the area occupied by the insulating phase (A) must be 40% or more and 80% or less. If the area occupied by the entire surface α is less than 40%, the antistatic performance may become unstable or the scratch resistance may be insufficient, and it may not be practical. On the other hand, if the area occupied by the entire surface α exceeds 80%, the antistatic performance will be insufficient, which is not preferable. The design of the related conductive phase (B) and insulating phase (A) can be adjusted by controlling the compatibility of the resin material, adjusting the coating and drying conditions, and adjusting the blending amount and particle size of the filler material when using filler materials. In addition, the specific measurement method for each area, the preferable coating composition, and the manufacturing method will be described later. In addition, a particularly preferable range of the area occupied by the insulating phase (A) in the entire surface α is 40% or more and 60% or less.

Next, the change in haze before and after the wiping treatment of the resin film surface α of the present invention will be described. Here, the haze system means the value specified in JIS K 7136 (2000), and the film haze system is regarded as an index mainly showing the transparency of the film. If the surface of the film is scratched due to the wiping process, the transparency will decrease. Therefore, comparing the haze values before and after the wiping treatment is equivalent to evaluating the amount of surface scratches caused by the wiping treatment.

The change in haze on the surface α of the resin film of the present invention before and after the wiping treatment is performed under the conditions described below is preferably 3.0% or less. When it exceeds 3.0%, insufficient coating film hardness, insufficient film forming properties, or insufficient formation of the insulating phase (A) described later may occur. As a result, not only the scratch resistance is insufficient, but also the antistatic property becomes unstable, especially The antistatic performance is prone to change due to the conditions of exposure to oxygen, resulting in insufficient Stability situation. In addition, specific wiping treatment methods and haze measurement methods will be described later. More preferably, less than 2.5%, and particularly better, less than 1.9%.

Furthermore, the surface resistivity of the resin film surface α of the present invention must be 1×10 ¹⁰ Ω/□ or less. The surface resistivity is a value obtained by the measurement method described later, and is an index indicating the average conductivity of the resin film surface in a larger range than the measurement in the aforementioned conductivity measurement mode using AFM. If the surface resistivity exceeds 1×10 ¹⁰ Ω/□, the proportion of the aforementioned insulating phase (A) may be too large, or the performance of the conductive phase (B) may be insufficient, and sufficient antistatic performance may not be obtained. The measurement method of related surface resistivity will be described later. The surface resistivity is preferably 1×10 ⁹ Ω/□ or less, more preferably 1×10 ⁷ Ω/□ or less. On the other hand, the relevant lower limit is not particularly limited, and from the viewpoint of film forming properties and cost, the practical configuration is preferably 1×10 ⁴ Ω/□ or more.

[Resin film and laminated resin film]

The resin constituting the resin film of the present invention is not particularly limited, and examples thereof include well-known acrylic resins, polyester resins, urethane resins, melamine resins, and epoxy resins. In the present invention, acrylic resin and melamine resin are preferred from the viewpoint of stability when produced by a preferred production method described later.

The resin film of the present invention may be a single-layer film or a multilayer film provided that at least one of the surfaces is provided with a surface α that satisfies the aforementioned conditions. It may also be provided with a layer formed on at least one or both sides of the supporting substrate.

Here, the term "layer" in the present invention refers to a discontinuous boundary surface, such as the composition of constituent elements, the shape of particles and other contents, and the physical properties in the thickness direction, between the surface of the laminate and the adjacent part in the thickness direction. , The limited thickness parts distinguished. More specifically, it refers to the use of various composition/element analysis devices for the above-mentioned laminates. Set (FT-IR, XPS, XRF, EDAX, SIMS, EPMA, EELS, etc.), electron microscope (transmission, scanning) or optical microscope, when cross-sectional observation from the surface to the thickness direction, use the above discontinuous boundary surface Distinguish the parts with limited thickness.

[Layer (X)]

From the viewpoint of antistatic properties and scratch resistance, the resin film of the present invention preferably has a layer (X) provided on at least one surface of the supporting substrate, and the layer (X) preferably has the aforementioned surface α. As the resin constituting the layer (X), it is preferable to use resins exemplified for the resin constituting the aforementioned resin film. The method for forming layer (X) is provided that the aforementioned conditions are met, and the rest is not particularly limited, and it is preferably formed by a coating composition. The coating composition described later may be applied to the support substrate during film formation to form a film, or after the support substrate is formed into a film, the coating composition may be applied to the support substrate, followed by drying and winding.

For example, when the layer (X) is formed by coating, the thickness of the layer (X) (the coating thickness after drying) is preferably 10 to 2000 nm, more preferably 40 to 1000 nm, particularly preferably 80 to 800 nm. If the thickness is 10 nm to 2000 nm, the functions (that is, antistatic property, scratch resistance) and the quality of the coating film to be imparted by the utilization layer (X) can be obtained, which is preferable.

[Measurement of conductivity using AFM]

In the resin film of the present invention, when at least one surface is measured by a conductive AFM, a conductive phase (B) and an insulating phase (A) are observed. Here is a brief description of the conductivity measurement performed by an atomic force microscope. The atomic force microscope uses a cantilever with a sharp tip at the atomic scale to measure the uneven shape by scanning the surface shape. The measurement uses a conductive cantilever to detect the surface of the film by applying a voltage between the cantilever and the sample. The faint current, and the image. Call this measurement Conductivity measurement mode or conductive AFM (Conductive AFM: c-AFM). When conducting AFM measurement, it can detect the fine current (tunneling current) that surpasses the insulating air layer and can efficiently detect the slight difference in conductivity (the surface conductivity of the film) in the tiny area directly under the cantilever. Details and measurement methods will be described later.

In the surface α of the resin film of the present invention, the shape of the region formed by the insulating phase (A) has a preferable range. Specifically, the average area diameter of the insulating phase (A) on the surface α is preferably 50 nm or more and 200 nm or less, more preferably 50 nm or more and 100 nm or less. If the average area diameter of the insulating phase (A) is less than 50 nm, the scratch resistance may decrease and the antistatic performance may become unstable. On the other hand, if the average domain diameter of the insulating phase (A) exceeds 200 nm, the formation of conductive paths may be hindered, and as a result, sufficient antistatic properties may not be obtained. As a method of controlling the average domain diameter, when a metal oxide is used as a constituent material of the insulating phase (A) in a preferable coating composition described later, the particle diameter can be controlled.

[The conductive phase (B) of electrically conductive I _B, and the insulating phase (A) of electrically conductive I _A]

When the resin film of the present invention is measured by conductive AFM, the obtained current value (conductivity index) has a preferable numerical range. Specifically, the ratio I _B /I _A of the conductivity I _B of the conductive phase (B) and the conductivity I _B of the insulating phase (A) is preferably 100 or more and 100000 or less, more preferably 3000 or more and Below 100,000. If the conductivity ratio I _B /I _{A is} less than 100, the separation structure of the insulating phase (A) and the conductive phase (B) will be insufficient, resulting in insufficient scratch resistance or unstable antistatic performance Happening. On the other hand, the relevant upper limit is not particularly limited, and it is preferably 100,000 or less. The relevant details and measurement methods will be described later.

[Measurement of elastic modulus using AFM]

Furthermore, the surface α of the resin film of the present invention has a preferable range of elastic modulus measured by an atomic force microscope. Specifically, the insulating phase (A) of the elastic modulus G _A preferred system 50000MPa 2000MPa or more and less, and more preferably 5000MPa or more based 20000MPa less. If it is less than 2000 MPa, the aforementioned scratch resistance may not be obtained, and the stability of antistatic performance may not be obtained. On the other hand, if it exceeds 50,000 MPa, the film processability such as cracks may easily occur during film processing and may decrease.

Further, the surface of the resin film of the present invention, α, the insulating phase (A) an elastic modulus G _A, the conductive phase (B) elastic modulus ratio G _B G _A / G _B, also there is a preferred range. Specifically, G _A /G _{B is} preferably 4 or more and 20 or less, more preferably 6 or more and 16 or less, and particularly preferably 8 or more and 12 or less. If G _A /G _{B is} less than 4 or more than 20, because the hardness of the resin film is biased toward the soft side or the hard side, it may be difficult to balance scratch resistance and processability.

Furthermore, in the resin film surface α of the present invention, the elastic modulus G _{B of the} conductive phase (B) is preferably 500 MPa or more and 2000 MPa or less. If it is less than 500 MPa, the scratch resistance of the resin film may decrease, and if it exceeds 2000 MPa, the processability may decrease.

The elastic modulus measurement performed by the atomic force microscope here is a compression test using a very small part of the probe. Because it belongs to the degree of deformation caused by the pressing force, the cantilever with a known elastic constant can be used to determine the surface α Elastic modulus and spatial distribution. Specifically, in the aforementioned conductivity measurement, the elastic modulus information of each area can be obtained by measuring the force curve described later in each area detected as the conductive phase (B) or the insulating phase (A). The details are described in the examples, use the following In the atomic force microscope, the probe at the tip of the cantilever is in contact with the surface α, and the force curve is measured by pressing force of 55nN to measure the deflection of the cantilever. In addition, the correlation spatial resolution at this time depends on the scanning range and the number of scanning lines of the atomic force microscope, but the actual measurement conditions have a lower limit of about 50 nm. Related details and measurement methods will be described later.

[Supporting substrate, polyester film]

As mentioned above, the resin film of the present invention may be a single-layer film or a laminated film. The preferred form is a resin film laminated with a supporting substrate and a layer (X) with a surface α on at least one of its surfaces. . The resin used as the supporting substrate is not particularly limited, but from the viewpoint of heat resistance and cost, it may be, for example, polyester. The supporting substrate is preferably a layer mainly composed of polyester (hereinafter also used as a supporting substrate, and a layer mainly composed of polyester is referred to as "polyester film"). In addition, the main component in the present invention refers to a component that accounts for 50% by weight or more with respect to the entire resin constituting the layer.

In the present invention, the particle content of the supporting substrate is preferably 0.1% by weight or less with respect to the entire supporting substrate. By setting the particle content within the above range, the internal haze can be set to 0.2% or less, and a resin film with excellent transparency can be obtained.

Hereinafter, the polyester used for the supporting substrate of the resin film of the present invention will be described. First of all, the so-called polyester-based main chain is a general term for polymers with ester bonds, and preferably ones can be used from: ethylene terephthalate, propylene terephthalate, and ethylene 2,6-naphthalate , Butylene terephthalate, Propylene 2,6-Naphthalate, Ethylene-α,β-bis(2-chlorophenoxy)ethane-4,4'-dicarboxylate, etc. Choose at least one as a constituent.

The polyester film using the above-mentioned polyester is preferably biaxially aligned. So-called dual axis Oriented polyester film generally refers to stretch the unstretched polyester sheet (or film) in the longitudinal direction and the width direction orthogonal to the longitudinal direction by 2.5 to 5 times respectively, and then heat treatment to complete the crystallization Aligners, those who present biaxial alignment patterns when using wide-angle X-ray diffraction. When the polyester film is biaxially aligned, the thermal stability (especially dimensional stability, mechanical strength) is sufficient, and the flatness is also good.

Furthermore, various additives such as antioxidants, heat stabilizers, weather stabilizers, ultraviolet absorbers, organic slip agents, pigments, dyes, organic or Inorganic particles, fillers, antistatic agents, nucleating agents, etc.

The thickness of the polyester film is not particularly limited. It can be appropriately selected according to the application and type. From the viewpoints of mechanical strength and operability, it is generally preferably 10 to 500 μm, more preferably 15 to 250 μm, and particularly preferably 20 ~200μm. In addition, the polyester film system may be a composite film formed by co-extrusion, or may be a film bonded by various methods from the obtained film.

[Manufacturing method of resin film]

Regarding the manufacturing method of the resin film of the present invention, the following examples are illustrated for description, but the materials, usage amount, ratio, processing content, processing order, etc. shown below can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be limitedly interpreted by the examples shown below.

The resin film of the present invention is formed by coating a coating composition containing metal oxide particles (a) and a binding component on a polyester film. When the coating composition contains a solvent, it is formed on the polyester film by drying the solvent Layer (X) can be obtained by this.

Furthermore, in the present invention, when it is desired to make the coating composition contain a solvent, The agent is preferably an aqueous solvent (to form an aqueous paint). If a water-based solvent is used for the solvent system, rapid evaporation of the solvent during the drying step can be suppressed, and not only a uniform composition layer can be formed, but it is also excellent from the viewpoint of environmental load.

Here, the so-called water-based solvent refers to, for example, water, or a combination of water, alcohols such as methanol, ethanol, isopropanol, butanol, ketones such as acetone, methyl ethyl ketone, ethylene glycol, diethylene glycol, propylene glycol, etc. Alcohols and other organic solvents soluble in water, mixed in any ratio.

In addition, the method of making the metal oxide particles (a) and the binding component into a water-based coating can be, for example, a method of making the metal oxide particles (a) or the binding component contain a hydrophilic group such as carboxylic acid or sulfonic acid; using emulsification The agent implements an emulsion method.

The coating method for coating the coating composition (x) on the polyester film is preferably an in-line coating method. The so-called continuous coating method is a method of applying coating in the production steps of the polyester film. Specifically, the method of applying coating at any stage from after the polyester resin is melt-extruded until the biaxially stretched post-heat treatment and coiling is performed, is usually applied to, for example: The substantially amorphous state obtained by quenching is not stretched (unaligned) polyester film (A film), or uniaxially stretched (uniaxially aligned) polyester film (B film) that is then stretched in the longitudinal direction, or further On any film such as a biaxially stretched (biaxially aligned) polyester film (C film) before heat treatment that stretches in the width direction.

In the present invention, it is best to coat the coating composition on any polyester film of the A film and B film before the crystallization is completed, and then stretch the polyester film in the uniaxial direction or the biaxial direction, using a relatively solvent A method of performing heat treatment at a higher boiling point to complete the crystal alignment of the polyester film while simultaneously setting the layer (X) and the surface α. According to this method, the production of polyester film and the coating and drying of the coating composition can be performed simultaneously (That is, the layer (X) is formed), so there is an advantage in manufacturing cost. In addition, by performing the extension after coating, the aggregation state of the metal oxide particles (a) in the layer (X) can be controlled, and the area and area diameter of the insulating phase (A) can be designed to improve Scratch resistance and antistatic properties.

In particular, the method of coating the coating composition on a film (B film) uniaxially stretched in the longitudinal direction, and then stretched in the width direction and heat-treated is more excellent. The reason is that compared with the method of applying biaxial stretching after coating on an unstretched film, since the stretching step is less once, defects and cracks caused by the composition layer due to stretching are less likely to occur, and transparency can be formed , A composition layer with excellent smoothness and antistatic properties.

Furthermore, by using the continuous coating method to provide the layer (X), by applying the extension treatment after coating the coating composition, the surface arrangement of the metal oxide particles (a) can be promoted, and the metal oxidation can be promoted The particles (a) become anisotropic agglomerates. As a result, the shape of the insulating phase (A) of the layer (X) can be optimized and antistatic properties can be exhibited. At the same time, it can also improve scratch resistance, processability, and And antistatic performance shows good stability against changes with time and humidity.

Since the layer (X) of the present invention has the above-mentioned various advantages, it is preferably provided by a continuous coating method. Here, the coating method of coating the coating composition on the polyester film can be a well-known coating method, for example: bar coating method, reverse coating method, gravure coating method, die coating method, knife coating method Any way.

In the present invention, the best layer (X) formation method is a method in which a coating composition using an aqueous solvent is applied to a polyester film by a continuous coating method, followed by drying and heat treatment. Furthermore, it is more preferable to use a method of continuously applying the coating composition on the uniaxially stretched B film. In the method of manufacturing the resin film of the present invention, dry The drying system can be implemented in the temperature range of 80~130℃ in order to complete the solvent removal of the coating composition. In addition, the heat treatment can be performed in the temperature range of 160~240°C for the purpose of completing the crystal alignment of the polyester film and completing the thermal curing of the coating composition to complete the formation of the layer (X). By changing the temperature and time of the high-temperature heat treatment, the better elastic modulus of the insulating phase (A) and the conductive phase (B) can be adjusted, so that the scratch resistance and processability can be improved.

Next, with regard to the method of manufacturing the resin film of the present invention, a case where a polyethylene terephthalate (hereinafter referred to as "PET") film is used as the polyester film will be described as an example, but it is not limited to this. First, after fully vacuum-dried PET pellets, they were supplied to an extruder, melt-extruded at about 280°C to form a sheet, and cooled and solidified to produce an unstretched (unaligned) PET film (A film). The film was stretched 2.5 to 5.0 times in the longitudinal direction using a roll heated to 80 to 120°C to obtain a uniaxially oriented PET film (B film). On one side of the B film, the coating composition of the present invention prepared to a predetermined concentration is applied.

At this time, before coating, surface treatment such as corona discharge treatment may be performed on the coating surface of the PET film. By performing surface treatments such as corona discharge treatment, the wettability of the coating composition to the PET film can be improved, and the coating composition can be prevented from being snapped, so that a uniform coating thickness layer (X) can be obtained. After coating, the end of the PET film is held by a clamp and introduced into a heat treatment zone (preheating zone) at 80~130°C to dry the solvent of the coating composition. After drying, stretch it by 1.1 to 5.0 times in the width direction. Then, it is introduced into a 160-240°C heat treatment zone (heat-fixing zone), and heat treatment is performed for 1-30 seconds to complete the crystal alignment.

In this heat treatment step (heat fixing step), if necessary, a relaxation treatment of 3 to 15% may be performed in the width direction or the longitudinal direction. The resin film thus obtained will It becomes a resin film excellent in transparency, scratch resistance, and antistatic properties.

In addition, the resin film of the present invention may be provided with an intermediate layer between the layer (X) and the supporting substrate. When the intermediate layer is provided, the layer of the present invention may be provided when the film of the laminated intermediate layer is rolled up, or thereafter. (X) In the previous steps, the film may be scratched. Therefore, in the present invention, it is preferable that the layer (X) and the supporting substrate are directly laminated.

The composition of the supporting substrate of the resin film of the present invention is not limited, and it can be, for example, a single-layer composition consisting of only A layer, or a multilayer composition of A layer/B layer (ie, two-layer multilayer composition), A layer/B layer /A layer structure (i.e. 2 types of 3-layer laminated structure), A layer/B layer/C layer structure (i.e., 3 types of 3-layer laminated structure, etc.).

The method of laminating the supporting substrate of the resin film of the present invention is not limited. For example, the method of laminating by coextrusion, the method of laminating by laminating, the method of combining these, etc., are based on transparency and From the viewpoint of manufacturing stability, it is preferable to adopt a co-extrusion method. When forming a laminate, for the purpose of imparting different functions to each layer, a different resin composition may be used. For example, when the layer A/layer B/layer A is composed of laminated layers (ie, two types of three-layer laminated structure), from the perspective of transparency, for example, the B layer is composed of homopolyethylene terephthalate, and Methods such as adding particles in order to impart slipperiness to the A layer.

[Coating composition]

The layer (X) of the resin film of the present invention is preferably produced by applying the coating composition constituting the layer (X) to at least one side of the supporting substrate and then subjecting it to heat treatment. The specific paint composition may contain metal oxide particles, acrylic resin, binder resin, and conductive compound. In addition to the above-mentioned components, various additives may be contained. Hereinafter, the preferred form of the components contained in the coating composition will be described in detail.

[Metal oxide particles (a)]

In the resin film of the present invention, the insulating phase (A) preferably contains metal oxide particles (a). The metal oxide particles (a) contain at least one metal element selected from the group consisting of Si, Al, Ti, Zr, Se, and Fe. By containing the metal oxide particles (a), a nano-concave-convex structure can be formed on the surface of the resin film, and the smoothness is optimized and the scratch resistance is also excellent. Specific examples of the metal oxide particles (a) used in the resin film of the present invention include: silica (SiO ₂ ), alumina (Al ₂ O ₃ ), titanium dioxide (TiO ₂ ), and zirconium dioxide (ZrO ₂ ), selenium dioxide (SeO ₂ ), iron oxide (Fe ₂ O ₃ ) particles, etc. These systems may be used individually by 1 type, and may use 2 or more types together.

In particular, if the metal oxide particles (a) use titanium oxide (TiO ₂ ) particles, aluminum oxide (Al ₂ O ₃ ) particles, or zirconium oxide (ZrO ₂ ) particles, it is possible to suppress the interference spots of the resin film. Scratch resistance is better.

If the metal oxide particles (a) used in the resin film of the present invention have a particle size of 10 to 100 nm, the surface of the resin film can be used to form a dense nano-concave-convex structure to disperse the frictional force, resulting in scratch resistance Excellent, so better. In addition, the particle size of the metal oxide particles (a) of the present invention refers to the particle size determined by a scanning electron microscope (SEM) according to the following method.

(Method for obtaining the particle size of metal oxide particles (a))

A microtome was used to cut the surface of the resin film in a vertical direction to form small pieces, and a scanning transmission electron microscope (SEM) was used for the cross-section of the resin film. From the cross-sectional photograph, image analysis software Image-Pro Plus (Roper Co., Ltd., Japan) was used to obtain the particle size distribution of the particles present in the film. Sectional photos are different Select from any measurement field of view, and then measure the diameter (equivalent circle diameter) of more than 200 particles arbitrarily selected from the cross-sectional photos. The horizontal axis is the particle size and the vertical axis is the particle existence ratio. distributed. In the above-mentioned volume-based particle size distribution, the particle size indicated by the horizontal axis starts from 0nm and the scale is every 10nm, and the particle existence ratio indicated by the vertical axis is calculated by the formula "existence ratio=total number of detected particles with this particle diameter Volume/total volume of total detected particles" is indicated. From the graph of the particle existence ratio obtained as described above, the reading indicates the extremely large peak top particle size.

The metal oxide particles (a) used in the resin film of the present invention are preferably a composition (AD) having an acrylic resin (D) on part or all of the surface of the metal oxide particles (a). By setting the composition (AD) with acrylic resin (D), the metal oxide particles (a) in the resin film can be dispersed in nanometers. When force is applied to the resin film, the force can be dispersed in particle. As a result, the scratch resistance of the resin film can be improved. In addition, the transparency of the resin film can also be maintained, which is preferable.

In order to obtain a composition (AD) in which part or all of the surface of the metal oxide particles (a) has an acrylic resin (D), for example, the metal oxide particles (a) described later can be surface-treated with an acrylic resin (D) Methods etc. Specifically, the following methods (i) to (iv) can be exemplified. In addition, in the present invention, the term “surface treatment” refers to a treatment in which all or part of the surface of the metal oxide (a) having a specific element adsorbs/attaches the acrylic resin (D).

(i) A method in which a mixture of metal oxide particles (a) and acrylic resin (D) is mixed in advance, added to a solvent, and then dispersed.

(ii) A method in which metal oxide particles (a) and acrylic resin (D) are sequentially added and dispersed in a solvent.

(iii) Disperse metal oxide particles (a) and acrylic acid in a solvent in advance Resin (D), and then mixing the obtained dispersion.

(iv) A method of adding the acrylic resin (d-2) to the obtained dispersion after dispersing the metal oxide particles (a) in a solvent.

The intended effect can be obtained by using any of these methods.

Furthermore, the device for performing dispersion can use, for example: high-speed mixer, high-speed mixer, homomixer, kneader, ball mill, roller mill, sand mill, paint shaker, SC grinding disc, ring mill , Pin-type mill, etc.

Furthermore, the dispersion method uses the above-mentioned device to make the rotating shaft rotate at a peripheral speed of 5 to 15 m/s. The rotation time is 5~10 hours.

Furthermore, when dispersing, from the viewpoint of improving dispersibility, it is more preferable to use dispersed beads such as glass beads. The ball diameter is preferably 0.05~0.5mm, more preferably 0.08~0.5mm, particularly preferably 0.08~0.2mm.

The method of mixing and stirring can be, for example, shaking the container by hand, or using a magnetic stirrer, stirring blade, or performing ultrasonic irradiation, vibration dispersion, and the like.

In addition, whether or not the acrylic resin (D) is adsorbed/adhered to all or part of the surface of the metal oxide particles (a) can be confirmed by the following analysis method. The object to be measured was subjected to centrifugal separation (rotation number 3,000 rpm, separation time 30 minutes) using a Hitachi desktop ultra-high-speed centrifuge (Hitachi Koki Co., Ltd.: CS150NX) to make the metal oxide particles (a) (and metal After the acrylic resin (D) adsorbed on the surface of the oxide particles (a) is precipitated, the supernatant liquid is removed, and the precipitate is concentrated and dried. The concentrated and dried precipitate was analyzed by X-ray photoelectron spectroscopy (XPS) to confirm the presence or absence of acrylic resin (D) on the surface of metal oxide particles (a). When it is confirmed that on the surface of the metal oxide particles (a), 100% by weight relative to the total of the metal oxide particles (a) is present. When the acrylic resin (D) reaches 1% by weight or more, it is considered that the acrylic resin (D) is adsorbed/adhered to the surface of the metal oxide particles (a).

[Acrylic (D)]

As described above, in the resin film of the present invention, the metal oxide particles (a) contained in the insulating phase (A) preferably have a composition (AD) having acrylic resin (D) in part or all of the surface. By using the composition (AD) with acrylic resin (D), the metal oxide particles (a) in the resin film can be nano-dispersed, and the transparency of the resin film can be maintained, and when the resin film is applied When the force is applied, the force can be dispersed in the particles. As a result, the scratch resistance of the resin film can be improved.

The acrylic resin (D) of the present invention preferably has: a monomer unit (d ₁ ) represented by formula ( ₁ ), a monomer unit (d ₂ ) represented by formula ( ₂ ), and a monomer unit represented by formula (3) Body unit (d ₃ ) resin.

[化1]

(In the formula (1), the R ₁ group represents a hydrogen element or a methyl group. In addition, the n system represents an integer of 9 or more and 34 or less.).

[化2]

(In formula (2), the R ₂ group represents a hydrogen element or a methyl group. In addition, the R ₄ group represents a group containing 2 or more saturated carbocyclic rings.).

[化3]

(In formula (3), the R ₃ group represents a hydrogen element or a methyl group. In addition, the R ₅ group represents a hydroxyl group, a carboxyl group, a tertiary amino group, a quaternary ammonium salt group, a sulfonic acid group, or a phosphoric acid group.)

Here, the acrylic resin (D) of the present invention is preferably a resin having a monomer unit (d ₁ ) represented by formula (1).

In formula (1), if an acrylic resin having a monomer unit with n less than 9 is used, the dispersibility of the metal oxide particles (a) in the aqueous solvent (the details of the relevant aqueous solvent will be described later) becomes unstable. If an acrylic resin having a monomer unit of formula (1) with n less than 9 is used, the metal oxide particles (a) in the coating composition will violently agglomerate, and the metal oxide particles may appear in the aqueous solvent depending on the situation (a) The situation of precipitation. As a result, the transparency of the resin film may be impaired, or it may become a protrusion and cause a disadvantage. On the other hand, acrylic resins having monomer units in which n exceeds 34 of the formula (1) have significantly low solubility in aqueous solvents, and therefore acrylic resins tend to aggregate in aqueous solvents. Since this aggregate is larger than the wavelength of visible light, it may not be possible to obtain a good transparent resin film, or when the coating film is further laminated on the surface layer of the laminated film of the present invention, interference spots may occur. By using a resin having the above formula (1) and the monomer units (D _1), the metal oxide particles (a) using the appropriate interaction in a dispersed state in an aqueous solvent, on the other hand, dried The latter plural metal oxide particles (a) have anisotropy and are finely aggregated at the nanometer level on the resin film, and form non-circular insulating regions on the surface of the resin film, thereby suppressing the exposure of conductive materials It can improve the resistance of antistatic property to changes over time.

The acrylic resin (D) of the present invention can have the monomer unit (d ₁ ) represented by the formula (1), and the (meth)acrylate monomer (d ₁ ') represented by the following formula (4) must be used as a raw material Perform polymerization.

The (meth)acrylate monomer (d ₁ ') is preferably a (meth)acrylate monomer represented by an integer of formula (4) where n is 9 or more and 34 or less, more preferably 11 or more and 32 or less (Meth)acrylate monomers, particularly preferably 13 or more and 30 or less (meth)acrylate monomers.

[化4]

The (meth)acrylate monomer (d ₁ ') is a (meth)acrylate monomer whose n of formula (4) is 9 or more and 34 or less, and the rest is not particularly limited. Specific examples can be given Such as: decyl (meth)acrylate, dodecyl (meth)acrylate, tridecyl (meth)acrylate, tetradecyl (meth)acrylate, 1-methyl (meth)acrylate Tridecyl ester, cetyl (meth)acrylate, stearyl (meth)acrylate, eicosanyl (meth)acrylate, behenyl (meth)acrylate, hexadecyl (meth)acrylate Tetraalkyl esters, trialkyl (meth)acrylates, etc., particularly preferred are dodecyl (meth)acrylate and tridecyl (meth)acrylate. One kind of these systems may be used, or a mixture of two or more kinds may be used.

Furthermore, the acrylic resin (D) of the present invention focuses on the resin having the monomer unit (d ₂ ) represented by the above formula (2).

In formula (2), if an acrylic resin having a monomer unit containing only one saturated carbocyclic ring is used, the function of the steric barrier is insufficient, and the metal oxide particles (a) may be aggregated or precipitated in the coating composition. There may be metal oxidation in the aqueous solvent (A) Precipitation of particles. As a result, the transparency of the resin film may be impaired, or it may become a protrusion and cause a defect.

Since this aggregate is larger than the wavelength of visible light, it may not be possible to obtain a resin film with good transparency. The acrylic resin (D) of the present invention can have the monomer unit (d ₂ ) represented by the formula (2), and the (meth)acrylate monomer (d ₂ ') represented by the following formula (5) must be used as a raw material Perform polymerization.

The (meth)acrylate monomer (d ₂ ') represented by formula (5) is for example: cross-linked condensed cyclic formula (having a structure in which two or more rings each share two elements and are bonded), spiro ring Formula (a structure in which one carbon element is shared and two ring structures are bonded) and other ring structures. Specific examples include compounds having a bicyclic, tricyclic, tetracyclic group, etc., among them, particularly from From the viewpoint of lipid compatibility with the binder, a (meth)acrylate containing a bicyclic group is preferred.

[化5]

The above-mentioned (meth)acrylates containing bicyclic groups include, for example, isobornyl (meth)acrylate, bornyl (meth)acrylate, dicyclopentyl (meth)acrylate, and bicyclic (meth)acrylate Pentenyl ester, adamantyl (meth)acrylate, dimethyladamantyl (meth)acrylate, etc., and isobornyl (meth)acrylate is particularly preferred.

Furthermore, the acrylic resin (D) of the present invention is preferably a resin having a monomer unit (d ₃ ) represented by the above formula (3).

If an acrylic resin in which the R ₅ group of formula (3) does not have a monomer unit of any one of a hydroxyl group, a carboxyl group, a tertiary amino group, a quaternary ammonium group, a sulfonic acid group, and a phosphoric acid group is used, the acrylic resin is used in an aqueous solvent Insufficient compatibility in the coating composition may cause the precipitation of acrylic resin in the coating composition, or with this phenomenon, the metal oxide particles (a) may aggregate or precipitate, or the metal oxide particles (a) may aggregate during the drying step.

Since this aggregate is larger than the wavelength of visible light, it may not be possible to obtain a resin film with good transparency. Since the acrylic resin (D) of the present invention has the monomer unit (d ₃ ) represented by formula ( ₃ ), it is necessary to use the (meth)acrylate monomer (d ₃ ') represented by formula (6) as a raw material Perform polymerization.

The (meth)acrylate monomer (d ₃ ′) represented by the formula (6) can be exemplified by the following compounds.

[化6]

Examples of (meth)acrylate monomer systems with hydroxyl groups include: 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 2,3-(meth)acrylate Monoesters of polyols such as dihydroxybutyl, 4-hydroxybutyl (meth)acrylate, polyethylene glycol mono(meth)acrylate and (meth)acrylic acid; or to open ε-caprolactone The compound etc. which are cyclically polymerized to this monoester, especially 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate are preferable.

The (meth)acrylate monomer system with a carboxyl group can include, for example, α,β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, fumaric acid, and maleic acid; or (a (Base) Hydroxyalkyl acrylate, half esterified product with acid anhydride, etc., particularly preferably acrylic acid and methacrylic acid.

The single system containing tertiary amine groups can include, for example: (meth)acrylic acid-N,N-dimethylaminoethyl, (meth)acrylic acid-N,N-diethylaminoethyl, (methyl) )-N,N-dimethylaminopropyl acrylate and other (meth)acrylic acid-N,N-dialkylaminoalkyl esters; N,N-di Methylaminoethyl (meth)acrylamide, N,N-diethylaminoethyl (meth)acrylamide, N,N-dimethylaminopropyl (meth)acrylamide, etc.N , N-Dialkylaminoalkyl (meth)acrylamide, etc., particularly preferably -N,N-dimethylaminoethyl (meth)acrylate.

The quaternary ammonium salt group-containing monomer preferably uses a quaternary agent such as epihalohydrin, halogenated benzyl group, and halogenated alkyl group to act on the above-mentioned tertiary amine group-containing monomer. Specific examples include: 2- (Methacryloxy) ethyl trimethyl ammonium chloride, 2-(methacryloxy) ethyl trimethyl ammonium bromide, 2-(methacryloxy) ethyl trimethyl ammonium dimethyl phosphoric acid (Meth)acryloyloxyalkyl trialkylammonium salt; methacrylamidopropyltrimethylammonium chloride, methacrylamidopropyltrimethylammonium bromide, etc. (meth)acrylic acid Alkylamine alkyl trialkylammonium salt; tetrabutylammonium (meth)acrylate and other tetraalkyl (meth)acrylates; trimethylbenzylammonium (meth)acrylate and other trialkylbenzylammonium (meth) Acrylates and the like are particularly preferably 2-(methacryloxy)ethyltrimethylammonium chloride.

The sulfonic acid group-containing single system may include, for example, (meth)acrylamide-alkane sulfonic acid, such as butylacrylamide sulfonic acid, 2-acrylamide-2-methylpropanesulfonic acid; or (methyl) (Meth) sulfoalkyl acrylates such as 2-sulfoethyl acrylate, etc., particularly preferably 2-sulfoethyl (meth)acrylate.

Examples of the phosphoric acid group-containing acrylic monomer system include acid phosphooxyethyl (meth)acrylate, etc., and acid phosphooxyethyl (meth)acrylate is particularly preferred.

Among them, it is particularly preferable that the acrylic resin (D) has a monomer unit represented by the above formula (3) (d ₃ ) from the viewpoint of high adsorption force with the metal oxide particles (a) described later and capable of forming a stronger film. ), and the R ₅ group of formula (3) is a hydroxyl group or a carboxyl group.

The content of acrylic resin (D) in the resin film of the present invention is preferably 5 to 30% by weight. By setting it in this range, the metal oxide particles (a) and acrylic resin (D) can be adsorbed firmly , And can improve the scratch resistance of the resin film.

In particular, the content of acrylic resin (D) is more preferably 5% by weight or more and 30% by weight or less relative to the entire resin film. The acrylic resin (D) content in the resin film is particularly preferably 10% by weight or more and 30% by weight. %the following. In addition, in the present invention, the content in the resin film means the content in the solid content ([(coating composition weight)-(solvent weight)]) of the coating composition forming the resin film.

If the resin film of the present invention contains metal oxide particles (a) in the resin film at 15 to 50% by weight relative to the entire resin film, the resin film can be filled with metal oxide particles (a). Preventing the conductive material from being exposed on the surface of the resin film can easily stabilize the antistatic performance. In addition, by increasing the area of the particle component, the hardness of the entire resin film can be increased and the scratch resistance is excellent, which is preferable. The content rate of the metal oxide particles (a) is preferably 20 to 50% by weight, more preferably 30 to 50% by weight.

[Binder Resin]

The components of the resin film and layer (X) of the present invention preferably contain a binder resin. The so-called binder resin includes well-known acrylic resins, polyester resins, urethane resins, and copolymers of these.

The urethane resin system can use, for example, a resin having a structural unit derived from the polyisocyanate compound (I) and a polyol (II) unit. In addition, the polyurethane resin may have units other than the polyisocyanate compound (I) unit and the polyol (II) unit (for example, carboxylic acid unit, amine unit, etc.).

The polyurethane resin system can be, for example, polyacrylic polyurethane resin, polyether polyurethane resin, polyester polyurethane resin, and the like. The polyurethane resin system may be used individually by 1 type, and may use 2 or more types together.

The polyisocyanate compound (I) has 2 or more isocyanate groups As mentioned earlier, the rest is not particularly limited.

The polyisocyanate compound (I) series may include, for example: polyisocyanate (for example: aliphatic polyisocyanate, alicyclic polyisocyanate, aromatic aliphatic polyisocyanate, aromatic polyisocyanate, etc.), modified polyisocyanate [or derivative , For example: polymer (dimer, trimer, etc.), carbonyl diimide, biuret, allophanate, uretdione, polyamine modified body, etc.] etc. The polyisocyanate compound (I) system may be used individually by 1 type, and may use 2 or more types together. The aliphatic polyisocyanate is not particularly limited, and can be for example: aliphatic diisocyanate [e.g. alkane diisocyanate (e.g., tetramethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexa Methylene diisocyanate, dodecamethylene diisocyanate, lysine diisocyanate, 2-methylpentane-1,5-diisocyanate, 3-methylpentane-1,5-diisocyanate, etc. C2- 20 alkane diisocyanate, preferably C4-12 alkane diisocyanate, etc.)], aliphatic polyisocyanate with 3 or more isocyanate groups (for example: 1,4,8-triisocyanate octane and other aliphatic three to six Isocyanate, etc.) and so on.

烷二異氰酸酯等)等}、具有3以上異氰酸酯基的脂環 族聚異氰酸酯(例如：1,3,5-三異氰酸基環己酯等脂環族三至六異氰酸酯等)等。 The cycloaliphatic polyisocyanate is not particularly limited, and it can be for example: cycloaliphatic diisocyanate {e.g. cycloalkane diisocyanate (e.g. methyl-2,4- or 2,6-cyclohexane diisocyanate, etc. C5-8 Cycloalkane diisocyanate, etc.), isocyanato alkyl cycloalkane isocyanate [for example: isocyanate-3-isocyanatomethyl-3,5,5-trimethylcyclohexyl (isophorone two Isocyanate, IPDI) and other isocyanate C1-6 alkyl C5-10 cycloalkane isocyanate, etc.], bis(isocyanato alkyl) cycloalkane [e.g. hydrogenated diisocyanurate and other two ( Isocyanato C1-6 alkyl) C5-10 cycloalkyl ester], bis(isocyanato cycloalkyl) alkane [e.g. hydrogenated diphenylmethane-4,4'-diisocyanate (isocyanate- 4'4'-methylene bicyclohexyl ester) and other bis (isocyanate C5-10 cycloalkyl ester) C1-10 alkyl ester, etc.), polycycloalkane diisocyanate (lower

Alkyl diisocyanate, etc.), etc.}, alicyclic polyisocyanates having 3 or more isocyanate groups (for example, alicyclic three to hexaisocyanates such as 1,3,5-triisocyanatocyclohexyl, etc.).

Aromatic aliphatic polyisocyanates are not particularly limited, and can be, for example, aromatic aliphatic diisocyanates {e.g., bis(isocyanatoalkyl) aromatic hydrocarbons [e.g., xylene diisocyanate (XDI), diisocyanate) Tetramethylphenylene cyanate (TMXDI) (1,3- or 1,4-bis(1-isocyanato-1-methylethyl)benzene) and other bis(isocyanate C1- 6 alkyl) C6-12 aromatic hydrocarbons, etc.]}, aromatic aliphatic polyisocyanates with 3 or more isocyanate groups (for example: aromatic aliphatic three to six isocyanates, etc.).

The aromatic polyisocyanate is not particularly limited, and can be for example: aromatic diisocyanate {e.g. aromatic diisocyanate [e.g. o-, m- or p-phenylene diisocyanate, chlorophenyl diisocyanate, diisocyanate C6-12 aromatic diisocyanates such as toluene, naphthalene diisocyanate (NDI), etc.], bis(isocyanatoaryl)alkanes [for example: diphenylmethane diisocyanate (MDI) (2,4'-diphenylmethane two Isocyanate, 4,4'-diphenylmethane diisocyanate, etc.), toluidine diisocyanate and other bis(isocyanate C6-10 aryl) C1-10 alkane, etc.)), aromatic polycarbonate with 3 or more isocyanate groups Isocyanates (for example, aromatic three to hexaisocyanates such as 4,4'-diphenylmethane-2,2',5,5'-tetraisocyanate, etc.) and the like.

In the present invention, from the viewpoint of crack resistance, the polyisocyanate compound (I) is preferably an alicyclic polyisocyanate.

The polyol (II) is added before having 2 or more hydroxyl groups, and the rest is not particularly limited.

The polyol (II) system may be, for example, polyacrylic polyol ester, polyester polyol, polyether polyol, polyurethane polyol, and the like. The polyol (II) system may be used individually by 1 type, and may use 2 or more types together.

Polyacrylic acid polyol ester series such as: (meth)acrylate monomer Copolymers, etc., with a unit derived from a component having a hydroxyl group (a component unit having a hydroxyl group). Polyacrylic acid polyol ester may have units other than a (meth)acrylate unit and a component unit having a hydroxyl group.

The polyester polyol system may, for example, have a polycarboxylic acid component unit, a copolymer with a polyol component unit, and the like. The polyester polyol may have units other than the polycarboxylic acid component unit and the polyol component unit.

The polyether polyol system can be, for example, a copolymer obtained by adding alkylene oxide to a polyol. The polyol is not particularly limited, and for example, the above-mentioned diols and the like can be used. A polyol system may be used individually by 1 type, and may use 2 or more types together.

In addition, the alkylene oxide is not particularly limited, and examples thereof include alkylene oxides having 2 to 12 carbon atoms such as ethylene oxide, propylene oxide, and butylene oxide. An alkylene oxide system may be used individually by 1 type, and may use 2 or more types together. The constituent components of the polyurethane resin may contain a chain extender (or may have a structural unit derived from the chain extender).

The chain extender is not particularly limited. For example, glycols (for example, C2-6 alkanediols such as ethylene glycol, 1,4-butanediol, neopentyl glycol, and 1,6-hexanediol) can be used. ), polyols (for example: glycerol, trimethylolpropane, pentaerythritol and other C2-6 alkanes three to six alcohols), diamines (for example: ethylene diamine, hexamethylene diamine, etc.) and other general Chain extender.

The resin film or layer (X) of the present invention preferably contains an ether component. By containing the ether component, because of the high flexibility of the polyether structure, the stress generated during processing can be relieved, and the processability can be improved.

Furthermore, the resin film of the present invention preferably contains an ether component and a urethane component. If the resin film or layer (X) contains a urethane component and an ether component, the compatibility can be controlled. When the metal oxide particles (a) are contained in the resin film or layer (X) At this time, the insulating phase (A) can be easily formed on the surface of the resin film or layer (X). The method of making the resin film or layer (X) contain a urethane component and an ether component is not specifically limited, For example, the method of using the urethane resin component which has an ether bond can be used. Specifically, a urethane resin obtained by reacting a polyether polyol compound and an isocyanate compound is preferable. In addition, in the present invention, "a component having an ether" means having an ether bond, and a "a component having a urethane" means having a urethane bond.

If the above-mentioned urethane resin component is used, the hydrophilicity of the urethane resin component improves. Therefore, when it contains: metal oxide particles (a) [or a composition (AD) with acrylic resin (D) on part or all of the surface of the metal oxide particles (a)], and a urethane resin component The coating composition (x) is applied to at least one side of the polyester film to be the supporting substrate, and then heated to form the layer (X), which can form a highly hydrophilic urethane resin component in Layer (X) will be skewed on the polyester film side of the substrate layer, and the metal oxide particles (a) with lower hydrophilicity [or part or all of the surface of the metal oxide particles (a) have acrylic resin The composition (AD) of (D)] is concentrated in the phase separation structure near the surface of the layer (X). By having a phase separation structure in which the metal oxide particles (a) are near the surface of the layer (X) and the urethane resin component is concentrated in the vicinity of the interface between the layer (X) and the substrate layer, it can be A region with a high elastic modulus (island component) is formed near the surface of the layer (X), so scratch resistance can be expressed, and the inner layer of the layer (X) uses a soft urethane resin component to generate stress relaxation, It exhibits workability, so it can balance scratch resistance and workability at a high level, so it is preferable.

[Conductive compound (b)]

The conductive phase (B) component of the resin film of the present invention preferably contains a conductive compound (b). The conductive compound (b) is not particularly limited. For example, carbon nanotubes can be used (Carbon nano-tube: CNT) and other carbon-based materials, polymer materials having a conductive structure such as polythiophene structure, acidic polymers in a free acid state, etc., these systems can be used as monomers or in combination. From the viewpoint of the initial characteristics of antistatic performance, it is preferably a compound having a polythiophene structure and a mixed component of a free acid state acidic polymer.

As the compound system having a polythiophene structure, for example, compounds having a structure where the 3-position and 4-position positions of the thiophene ring are substituted, and the like can be used. Furthermore, it is preferable to use a compound in which the carbon atoms at the 3 and 4 positions of the thiophene ring are bonded to an oxygen atom. If a hydrogen atom or a carbon atom is directly bonded to the carbon atom, the coating liquid may not easily become water-based. The above-mentioned compound can be produced by, for example, the methods disclosed in Japanese Patent Laid-Open No. 2000-6324, European Patent No. 602713, and US Patent No. 5391472, and methods other than these can also be used.

For example, using the alkali metal salt of 3,4-dihydroxythiophene-2,5-dicarboxylate as the starting material to obtain 3,4-dioxyethylenethiophene, peroxygen is introduced into the aqueous solution of polystyrene sulfonic acid Potassium disulfate, iron sulfate, and the previously obtained 3,4-dioxyethylene thiophene can be reacted to obtain acidic polymers such as polystyrene sulfonic acid, and the complex is converted to poly(3,4-dioxyethylene thiophene). Oxyethylene thiophene) and other polythiophene compositions.

In addition, the water-based paint composition containing poly-3,4-dioxoethylene thiophene and polystyrene sulfonic acid can be sold by H.C. Starck Company (Germany) under the trade name "Baytron" P, etc.

On the other hand, the acidic polymer in the free acid state can be, for example, polymer carboxylic acid, polymer sulfonic acid, polyvinyl sulfonic acid, and the like. The polymer carboxylic acid series can be, for example, polyacrylic acid, polymethacrylic acid, and polymaleic acid. In addition, the polymer sulfonic acid may be, for example, polystyrene sulfonic acid, and particularly from the viewpoint of antistatic properties, polystyrene sulfonic acid is preferred. In addition, the free acid can also form a salt form in which a part of it is neutralized. Also, it can also be used The form of copolymerization with other monomers that can be copolymerized (for example: acrylate, methacrylate, styrene, etc.). The molecular weight of polymer carboxylic acid and polymer sulfonic acid is not particularly limited. From the viewpoint of stability and antistatic properties of the coating agent, the weight average molecular weight is preferably 1,000 or more and 1,000,000 or less, more preferably 5,000 or more and 150,000 or less . As long as it does not hinder the characteristics of the invention, some of them may contain alkali salts such as lithium salts and sodium salts, ammonium salts, and the like. The salt in which the polyanion is neutralized can be considered as a dopant. The reason is that polystyrene sulfonic acid and ammonium salt, which have very strong acid functions, undergo an equilibrium reaction after neutralization, resulting in the equilibrium tending to the acid side.

[Other ingredients]

唑啉化合物、羰二醯亞胺化合物、異氰酸酯化合物、環氧化合物中選擇至少1種化合物的塗料組成物形成，則樹脂薄膜成為緻密交聯構造，因而耐刮傷性與抗靜電性能安定性優異，故較佳。所以，本發明樹脂薄膜的導電相(B)，較佳係含有源自例如：三聚氰胺化合物、

唑啉化合物、羰二醯亞胺化合物、異氰酸酯化合物、環氧化合物等的成分。 In the resin film of the present invention, if the conductive phase (B) is used containing from: melamine compound,

When the coating composition of at least one compound selected from the oxazoline compound, carbonyldiimide compound, isocyanate compound, and epoxy compound is formed, the resin film has a dense cross-linked structure, so it has excellent scratch resistance and antistatic performance and stability. , So better. Therefore, the conductive phase (B) of the resin film of the present invention preferably contains compounds derived from, for example, melamine,

Components such as oxazoline compounds, carbodiimide compounds, isocyanate compounds, and epoxy compounds.

唑啉化合物、羰二醯亞胺化合物的塗料組成物(x)，則樹脂薄膜中會被導入含氮官能基，因而極性力獲提升，在接著的加工中可提升與塗佈層、或濺鍍層、蒸鍍層等金屬層間之接著性，故較佳。 Especially if it contains melamine compound,

The coating composition (x) of the oxazoline compound and the carbonyl diimide compound will introduce nitrogen-containing functional groups into the resin film, so the polarity is improved, and the coating layer or sputtering can be improved in the subsequent processing. Adhesion between metal layers such as plating layer and vapor-deposition layer is preferable.

唑啉化合物、羰二醯亞胺化合物、異氰酸酯化合物 中選擇至少1種的塗料組成物(x)。 Furthermore, from the viewpoint of both conductivity, because related melamine compounds coexist with some conductive materials, the resistance value will increase, so it is best to use the following:

At least one coating composition (x) is selected from the oxazoline compound, carbonyldiimide compound, and isocyanate compound.

唑啉化合物、羰二醯亞胺化合物、異氰酸酯化合物、環氧化合物等交聯劑中選擇2種以上材料。藉由併用2種以上交聯劑，便可維持欲達導電性安定性、耐刮痕性提升時所必要的交聯性，且能降低個別材料的添加量，藉此可輕易賦予與樹脂成分間之相溶性。其中，較佳係使用含有從：

唑啉化合物、羰二醯亞胺化合物、異氰酸酯化合物中選擇至少2種的塗料組成物(x)。 On the other hand, when it is necessary to take into account optical properties such as transparency, it is best to use a combination of melamine compounds,

Two or more materials are selected from crosslinking agents such as oxazoline compounds, carbodiimide compounds, isocyanate compounds, and epoxy compounds. By using two or more cross-linking agents in combination, the necessary cross-linking properties can be maintained when the conductivity stability and scratch resistance are improved, and the added amount of individual materials can be reduced, thereby easily imparting resin components Compatibility between. Among them, it is better to use those containing from:

At least two coating compositions (x) are selected from the oxazoline compound, the carbonyldiimide compound, and the isocyanate compound.

與羥甲基的化合物。本發明的「三聚氰胺化合物」，係當下述三聚氰胺化合物係與胺基甲酸酯樹脂、丙烯酸樹脂、

唑啉化合物、或羰二醯亞胺化合物、異氰酸酯化合物、環氧化合物等形成交聯構造的情況，便指源自三聚氰胺化合物的成分。又，三聚氰胺系化合物係可由單體、二聚體以上的多聚體所構成縮合物中之任一者，亦可為該等的混合物。醚化所使用的低級醇係可使用例如：甲醇、乙醇、異丙醇、正丁醇、異丁醇等。1分子中所具有的基為亞胺基、羥甲基、或甲氧基甲基、丁氧甲基等烷氧甲基者，係可例如：亞胺基型甲基化三聚氰胺樹脂、羥甲基型三聚氰胺樹脂、羥甲基型甲基化三聚氰胺樹脂、完全烷基型甲基化三聚氰胺樹脂等。其中，較佳係羥甲基化三聚氰胺樹脂。又，為促進三聚氰胺系化合物的熱硬化，亦可使用例如對甲苯磺酸等酸性 觸媒。 For example, melamine-based compounds can be used: melamine, methylolated melamine derivatives obtained by condensation of melamine and formaldehyde, compounds that react methylolated melamine and lower alcohols to partially or completely etherify them, and these Mixture and so on. The specific preferably has three

Compounds with hydroxymethyl. The "melamine compound" of the present invention refers to the following melamine compound series and urethane resin, acrylic resin,

When an oxazoline compound, a carbonyldiimide compound, an isocyanate compound, an epoxy compound, etc. form a cross-linked structure, it means a component derived from a melamine compound. In addition, the melamine-based compound system may be any one of condensates composed of monomers, dimers or higher polymers, or may be a mixture of these. The lower alcohols used for etherification can be, for example, methanol, ethanol, isopropanol, n-butanol, isobutanol, etc. Groups in one molecule are imino groups, methylol groups, or alkoxymethyl groups such as methoxymethyl and butoxymethyl groups, such as: imino methylated melamine resins, methylol groups Base type melamine resin, methylol type methylated melamine resin, fully alkyl type methylated melamine resin, etc. Among them, methylolated melamine resin is preferred. In addition, in order to promote thermal curing of the melamine-based compound, an acidic catalyst such as p-toluenesulfonic acid may also be used.

If such a melamine-based compound is used, not only does the self-condensation of the melamine-based compound increase the hardness of the coating film, and the scratch resistance is improved, but also the hydroxyl and carboxyl groups contained in the acrylic resin react with the melamine-based compound. A stronger resin film can be obtained, and a film with excellent scratch resistance can be obtained.

唑啉化合物」係當下述

唑啉化合物、或由

唑啉化合物與胺基甲酸酯樹脂(d-2)、丙烯酸樹脂(D)、三聚氰胺化合物、異氰酸酯化合物、或羰二醯亞胺化合物等形成交聯構造的情況，便指源自

唑啉化合物的成分。

唑啉化合物係在該化合物中所具有官能基為

唑啉基之前提下，其餘並無特別的限定，較佳係由含有至少1種以上具

唑啉基單體，且與至少1種其他單體進行共聚合而獲得的含

唑啉基共聚合體構成者。 "

"Oxazoline compound" is as follows

Oxazoline compounds, or by

When the oxazoline compound forms a cross-linked structure with the urethane resin (d-2), acrylic resin (D), melamine compound, isocyanate compound, or carbonyl diimide compound, it is derived from

The component of the oxazoline compound.

The oxazoline compound has a functional group in the compound

The oxazoline group is mentioned before, and the rest is not particularly limited. It is preferably composed of at least one

Oxazoline-based monomer, and copolymerized with at least one other monomer containing

It is composed of oxazoline copolymers.

唑啉基單體係可使用例如：2-乙烯基-2-

唑啉、2-乙烯基-4-甲基-2-

唑啉、2-乙烯基-5-甲基-2-

唑啉、2-異丙烯基-2-

唑啉、2-異丙烯基-4-甲基-2-

唑啉、2-異丙烯基-5-乙基-2-

唑啉等，亦可使用該等中之1種或2種以上的混合物。其中，較佳係2-異丙烯基-2-

唑啉，亦容易工業性取得。 With

The oxazoline single system can be used for example: 2-vinyl-2-

Oxazoline, 2-vinyl-4-methyl-2-

Oxazoline, 2-vinyl-5-methyl-2-

Oxazoline, 2-isopropenyl-2-

Oxazoline, 2-isopropenyl-4-methyl-2-

Oxazoline, 2-isopropenyl-5-ethyl-2-

As for the oxazoline etc., you may use 1 type or the mixture of 2 or more types of these. Among them, 2-isopropenyl-2-

Oxazoline is also easy to obtain industrially.

唑啉化合物中，針對含

唑啉基單體所使用的至少1種其他單體，係在能與該含

唑啉基單體進行共聚合之單體前提下，其餘並無特別的限定，可使用例如：丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸丁酯、甲基丙烯酸丁酯、丙烯酸-2-乙基己酯、甲基丙烯酸-2-乙基己酯等丙烯酸酯或甲基丙烯酸酯類；丙烯酸、甲基丙烯酸、伊康酸、順丁烯二酸等不飽和羧酸類；丙烯腈、甲基丙烯腈等不飽和腈類；丙烯醯胺、甲基丙 烯醯胺、N-羥甲基丙烯醯胺、N-羥甲基甲基丙烯醯胺等不飽和醯胺類；醋酸乙烯酯、丙酸乙烯酯等乙烯酯類；甲基乙烯醚、乙基乙烯醚等乙烯醚類；乙烯、丙烯等烯烴類；氯乙烯、偏二氯乙烯、氟乙烯等含鹵-α,β-不飽和單體類；苯乙烯、α-甲基苯乙烯等α,β-不飽和芳香族單體類等等，可使用該等中之1種、或2種以上的混合物。

Among the oxazoline compounds, for those containing

At least one other monomer used in the oxazoline-based monomer is

Under the premise that the oxazoline-based monomer is copolymerized, the rest is not particularly limited. For example, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, methyl acrylate can be used. Acrylate or methacrylate such as butyl acrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, etc.; acrylic acid, methacrylic acid, itaconic acid, maleic acid, etc. Unsaturated carboxylic acids; Unsaturated nitriles such as acrylonitrile and methacrylonitrile; Unsaturated acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, etc. Amides; vinyl esters such as vinyl acetate and vinyl propionate; vinyl ethers such as methyl vinyl ether and ethyl vinyl ether; olefins such as ethylene and propylene; vinyl chloride, vinylidene chloride, vinyl fluoride, etc. Halogen-α,β-unsaturated monomers; α,β-unsaturated aromatic monomers such as styrene and α-methylstyrene, etc. One or two or more of these can be used mixture.

唑啉化合物等形成交聯構造的情況，便指源自羰二醯亞胺化合物的成分。「羰二醯亞胺化合物」係在該化合物的分子內具有1個或2個以上官能基為羰二醯亞胺基、或具有互異性關係之氰胺基的化合物前提下，其餘並無特別的限定。 The carbonyldiimide compound of the present invention is the following carbonyldiimide compound, or a carbonyldiimide compound, and a urethane resin, acrylic resin, melamine compound, isocyanate compound, or

When an oxazoline compound or the like forms a cross-linked structure, it refers to a component derived from a carbonyldiimide compound. "Carbondiimidin compound" is a compound that has one or more functional groups in the molecule of the compound, which are carbonyldiimidinyl groups or cyanamide groups that have a mutually heterogeneous relationship. The rest is nothing special. The limit.

A known technique can be used for the production of the oxodiimide compound. Generally, the carbonyldiimidate compound can be obtained by polycondensing a diisocyanate compound in the presence of a catalyst. The diisocyanate compound, which is the starting material of the carbonyl diimide compound, can be aromatic, aliphatic, alicyclic diisocyanate, etc., and the specific system can be, for example, toluene diisocyanate, diisocyanate diisocyanate, etc. Toluene, diphenylmethane diisocyanate, hexamethylene diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexyl diisocyanate, etc.

Example

[Characteristic measurement method and effect evaluation method]

The characteristic measurement method and effect evaluation method of the present invention are as follows.

(1) Measurement of surface α (1-1) Conductivity of surface α measured by AFM

The conductivity of the layer surface was measured using AFM (Dimension Icon manufactured by Burker Corporation), and analysis was performed using the conductivity measurement mode (conductive AFM). Specifically, according to the operating manual of the conductive AFM, the measurement was performed under the following conditions. In addition, the sample is fixed in accordance with the following method to ensure conductivity from the layer surface to the sample stage. First, the resin film is cut into a size of 1 cm x 1 cm. Next, on the stainless steel sample table, the resin film is arranged so that the surface of the conductive layer is facing upward. Furthermore, a conductive tape [Nissin EM Co., Ltd., carbon double-sided tape for SEM (aluminum substrate, width 8mm)] that can cover about 3 mm from the end of the resin film is fixed on the sample table.

Measuring device: Atomic Force Microscope (AFM) manufactured by Burker Corporation

Measurement mode: conductive AFM (conductive mode)

Cantilever: SCM-PIC manufactured by Bruker AXS

(Material: Si, elastic constant K: 0.2 (N/m), front-end curvature radius R; 20 (nm))

Measurement environment: 23℃‧in the atmosphere

Measuring range: 1 (μm) square

Resolution: 512×512

Cantilever moving speed: 10(μm/s)

Maximum press-in load: 10 (nN).

Applied voltage: 10V

After the measurement, select the "C-AFM Current" image, and use the "ScionImage" to binarize the image displayed on the screen [Maximum: 10nA, Minimum: 0pA, Threshold value 180 (set "black" to 0, "white" to 255, from black to white divided into 256 levels of gray scale, according to the flow of 10nA or more area is set to 255 (white), 0pA area is set to 0 (Black) mode is set to make a conductive image. In the obtained conductive image, the part with a higher current value shown in the gray scale above 180 is marked as white, and the current value shown in the gray scale is less than 180 The lower part is marked as black, and the colors are distinguished accordingly)] to obtain a conductive image of the surface α. In addition, the operation of binarization processing is performed in the above order, and the current value is 7.2 nA as the boundary value, and the image is divided into an insulating area and a conductive area.

(1-2) Existence of insulating phase (A) and conductive phase (B)

The 1 μm×1 μm conductive image obtained in (1-1) is divided into 40 vertical and horizontal directions, and divided into 1,600 25 nm×25 nm regions. Among the 1,600 areas, the case where all of the areas have both pure black and pure white is assumed to have an insulating phase (A) and a conductive phase (B). That is, the conductivity is not biased, when an image composed of only the insulating phase (A) is obtained, when an image composed of only the conductive layer (B) is obtained, or when the size of any phase is less than 25nm square , It is judged that there are no two phases including the insulating phase (A) and the conductive phase (B).

Furthermore, the measurement range is arbitrarily selected and the measurement is performed 10 times. If a black part and a white part are found 8 times or more, it is judged that there is an insulating phase (A) and a conductive phase (B).

(1-3) Conductivity of conductive phase (B) and insulating phase (A)

Among the 1600 regions of the conductive image obtained in (1-1), for all regions in the binarized image where the regions are completely black, the conductivity data is captured, and the average value is set as the insulating phase (A ) Conductivity (I _A ). Similarly, among the 1600 areas of the conductive image obtained in (1-1), the elastic modulus is measured for all areas where one area is completely pure white, and the average value is taken as the conductivity of the conductive phase (B) ( I _B ). In addition, the measurement range is arbitrarily selected and the measurement is performed 10 times, and the average value of the remaining 8 times except the maximum value and the minimum value is adopted.

(1-4) Area ratio of insulating phase (A)

For the conductive image obtained in (1-1), the area ratio of the black part is calculated using the Analize Particles function of the software (image processing software ImageJ/Developer: National Institutes of Health (NIH)) The total occupied area ratio is taken as the area ratio of the insulating phase (A).

(1-5) Average area diameter of insulating phase (A)

For the conductive image obtained in (1-1), the average area diameter of the black part will use the Analize Particles function of the software (image processing software ImageJ/Developer: National Institutes of Health (NIH)). The radius value calculated using the circle approximation is adopted as the average area diameter. In addition, the data processing at the end of the relevant measurement area is excluded from the measurement by enabling the Exclude on edges of Analize Particles (particle analysis).

(1-6) Insulation phase (A) with or without metal oxides (a)

Use SEM (Scanning Electron Microscope) to observe the surface of surface α at a magnification of 100,000 times, and then use EDX (Energy Dispersive X-ray Spectroscopy) to implement elements for the insulating phase (A) of surface α on the polyester film Analyze to determine whether metal oxide (a) is contained.

Specifically, for the insulating phase (A) of the surface α observed by Hitachi High-Tech Field Emission Scanning Electron Microscope (Model S-4800), the QUANTAX Flat QUAD System (Model Xflash 5060FQ) manufactured by BrukerAXS was used for element detection. When at least one metal element selected from the group consisting of Si, Al, Ti, Zr, Se, and Fe is detected, it is determined that the metal oxide (a) is contained.

In addition, when 50% or more of the insulating phase (A) of the surface α contains the metal oxide (a), it is judged that the insulating phase (A) of the surface α contains the metal oxide (a).

(1-7) The elastic modulus of surface α measured by AFM

The surface elastic modulus of the layer surface was measured using AFM (DimensionIcon manufactured by Burker Corporation), using the PeakForceQNM mode, and then using the attached analysis software "NanoScopeAnalysis V1.40" based on the JKR contact theory from the force curve obtained Analyze and obtain the surface elastic modulus.

Specifically, first, according to the PeakForceQNM mode operation manual, the cantilever warping sensitivity, elastic force constant, and tip curvature configuration are implemented. In addition, the spring force constant and the tip curvature will vary with each cantilever, so the measurement range is satisfied without affecting the measurement range: the spring force constant is 0.1 (N/m) or more and 0.4 (N/m) or less, and the tip curvature radius is 25 (nm) or less The conditions of the cantilever were measured. The measurement conditions are as follows:

Measuring device: Atomic Force Microscope (AFM) manufactured by Burker Corporation

Measurement mode: use Ramp mode to take force curve

Cantilever: SCM-PIC manufactured by Bruker AXS

(Material: Si, elastic constant K: 0.2 (N/m), front end curvature radius R: 20 (nm))

Measurement environment: 23℃‧in the atmosphere

Measurement times: 10 times

Cantilever moving speed: 10(μm/s)

Maximum press-in load: 10 (nN).

The Ramp mode is used for the measurement system. First, from the use of Scan mode, in accordance with the conductive phase (B) and insulating phase (A) obtained by the aforementioned conductivity measurement, determine the place to perform the measurement, and then use OFFSET to move to the center of the image. Next, switch to Ramp mode and implement the force curve.

Secondly, for the obtained force curve, the analysis software "NanoScopeAnalysis V1.40" is used for analysis to obtain the surface elastic modulus. The same measurement is repeated 10 times for each of the conductive phase (B) and the insulating phase (A), and the average value of the remaining 8 times except the maximum and minimum values is adopted as the elastic modulus G _A and G of each phase _B.

(2) Scratch resistance

After the wiping treatment was performed under the following conditions, the appearance of scratches on the surface of the resin film was visually confirmed, and the following evaluations were performed.

[Wipe treatment] The surface of the resin film was wiped back and forth with a load of 200 g/cm ² using iron fine velvet (PONSTAR #0000, manufactured by Nippon Steel Wool).

S: No scratches

A: 1~5 scratches

B: 6-10 scratches

C: 11~15 scratches

D: 16 or more scratches.

(3-1) Haze (transparency)

Haze measurement is performed under normal conditions (23°C, relative humidity 50%), after leaving the resin film sample for 40 hours, using Nippon Denshoku Industries Co., Ltd. turbidity meter "NDH5000", according to JIS K 7136 "Transparent Materials Haze Determination Method" (2000 version) was implemented. In addition, measurement was performed by irradiating light from one side of the laminated surface α of the sample. For the sample system, a total of 10 samples in a square with a side length of 50 mm were prepared, and each was performed once, and the measurement was performed 10 times in total, and the average value was taken as the haze value of the sample.

(3-2) Haze after wiping evaluation

After the wiping treatment was performed in the same manner as (2), the haze measurement was performed again in accordance with the above method.

(4) Interference spots

On the back of the laminated surface α of the resin film, stick a black glossy tape (made by YAMATO, PVC insulating tape No.200-50-21: black) so as not to get air bubbles.

The sample is placed in a dark room 30cm directly below a three-wavelength fluorescent lamp (international (stock) system, three-wavelength daylight color (FL 15EX-N 15W)), while changing the viewing angle, visually observe the degree of interference spots. Perform the following evaluations. Those who are above B are rated as "good".

A: Almost no interference spots are found

B: Some microscopic interference spots

C: The interference spots are strong.

(5) Antistatic performance (5-1) Initial antistatic property

50mm、反電極：

103mm)，依施加電壓100V施加10秒鐘後，施行測定。單位係Ω/□。評價樣品的表面α，將合計測定10次的平均值設為樣品的表面電阻率(R1)。 The antistatic property is measured by the surface resistivity. The surface resistivity is measured by placing the resin film to be measured at a relative humidity of 23% and 25°C for 24 hours. In this environment, a digital ultra-high resistance/micro ammeter R8340A and a resistivity test box 12702A (Advantest (Stock) system, main electrode:

50mm, counter electrode:

103mm), the measurement was performed after applying the applied voltage of 100V for 10 seconds. The unit is Ω/□. The surface α of the sample was evaluated, and the average value of 10 measurements in total was taken as the surface resistivity (R1) of the sample.

1×10 ⁸ Ω/□ or less is rated as good, 1×10 ¹⁰ Ω/□ or less is rated as a practical use level, and more than 1×10 ¹⁰ Ω/□ is rated as a practically problematic level.

(5-2) Antistatic after 1 month

After the resin film is formed, it is stored for 30 days in the state where the resin film is to be subjected to antistatic evaluation under the conditions of 23% relative humidity and 25°C, and then the evaluation is carried out according to the same method as (5-1). From the obtained value, find the rate of change with time [initial surface resistivity (Ω/□)/1 month later surface resistivity (Ω/□)], and evaluate the rate of change with time less than 3 times as " "Good", and rated those less than 10 times as "practical".

(5-3) Antistatic property when dry

The evaluation was carried out in the same manner as in (5-1), except that after the resin film was formed, it was allowed to stand at 105°C and 5% relative humidity for 1 hour, and then evaluated. [Surface resistivity during drying (Ω/□)/initial surface resistivity (Ω/□)] is preferably less than 1, and those less than 5 times are rated as "practical".

In addition, for the resin film obtained from the following examples and comparative examples Characteristics, etc. are organized in the table.

<Reference example> <Reference Example 1> An emulsion (EM-1) containing a composition (AD) of metal oxide particles (a) with acrylic resin (D) on the surface

A common acrylic resin reaction tank equipped with a stirrer, a thermometer, and a reflux cooling tube is filled with 100 parts by weight of isopropanol as a solvent, heated and stirred, and kept at 100°C.

Among them, dripped over 3 hours: (meth)acrylate (d'-1) n=19 eicosanyl methacrylate 40 parts by weight, (meth)acrylate (d'-2) A mixture of 40 parts by weight of isobornyl methacrylate having two rings and 20 parts by weight of 2-hydroxyethyl acrylate (meth)acrylate (d'-3) having other hydroxyl groups. Then, after the dropping is completed, heating is performed at 100°C for 1 hour, and then an additional catalyst mixture composed of 1 part by weight of 2-ethylhexanoic acid-tert-butyl peroxide is filled. Then, after heating at 100°C for 3 hours, cooling was performed to obtain acrylic resin (D-1).

The metal oxide particles (a) use metal oxide particles containing Al element "NanoTek" Al ₂ O ₃ slurry (manufactured by CI Kasei Co., Ltd. with a number average particle size of 60 nm: A-1), which are sequentially added to an aqueous solvent "NanoTek" Al ₂ O ₃ slurry and the above acrylic resin (D-1) are dispersed according to the following method to obtain a mixed composition (AD) containing metal oxide particles (a) and acrylic resin (D-1) Emulsion (EM-1). (The method of (ii) above.)

The addition amount ratio (weight ratio) of metal oxide particles (a) and acrylic resin (D-1) is set as (A)/(D-1)=50/50 (in addition, the weight ratio is the first decimal point It is obtained by rounding the digits). The dispersion treatment system is implemented with a homomixer, rotating at a peripheral speed of 10m/s for 5 hours. Implement. In addition, in the final composition (BA), the weight ratio of the metal oxide particles (a) to the acrylic resin (B) is (A)/(D-1)=50/50 (in addition, the weight ratio is a decimal point Round the first place).

In addition, the obtained composition (AD) was subjected to centrifugal separation (rotation number 3000 rpm, separation time 30 minutes) using a Hitachi tabletop ultrahigh-speed centrifuge (Hitachi Koki Co., Ltd.: CS150NX) to make metal oxide particles ( a) (and the acrylic resin (D) adsorbed on the surface of the metal oxide particles (a)) is precipitated, the supernatant liquid is removed, and the precipitate is concentrated and dried. The concentrated and dried precipitate was analyzed by X-ray photoelectron spectroscopy (XPS). As a result, it was confirmed that the acrylic resin (D) was present on the surface of the metal oxide particles (a). That is, the acrylic resin (D) is adsorbed/adhered on the surface of the metal oxide particles (a), and it is known that the obtained composition (AD) belongs to the metal oxide particles (a) and the acrylic resin (D) is provided on the surface particle of.

<Reference example 2> Emulsion (EM-2) containing metal oxide particles (a) with acrylic resin (D) on the surface (AD)

Except that the addition amount ratio (weight ratio) of the metal oxide particles (a) and acrylic resin (D-1) is changed to (A)/(D-1)=60/40, the rest are in accordance with the reference example 1 Similarly, EM-2 was obtained.

<Reference example 3> Emulsion (EM-3) containing metal oxide particles (a) with acrylic resin (D) on the surface (AD)

In addition to the addition amount ratio of the metal oxide particles (a) and the acrylic resin (D-1) (weight Except for changing the ratio to (A)/(D-1)=70/30, EM-3 was obtained in the same manner as in Reference Example 1.

<Reference example 4> Emulsion (EM-4) containing metal oxide particles (a) with acrylic resin (D) on the surface (AD)

Except for the metal oxide particles (a) which use Al-containing metal oxide particles ("NanoTek" Al ₂ O ₃ slurry (manufactured by CI Chemical Co., Ltd. with a number average particle size of 50 nm): A-2), the rest are all EM-4 was obtained in the same manner as in Reference Example 2.

<Reference example 5>

Emulsion (EM-5) containing metal oxide particles (a) with acrylic resin (D) on the surface (AD)

Except for the metal oxide particles (a) which use Al-containing metal oxide particles ("NanoTek" Al ₂ O ₃ slurry (manufactured by CI Kasei Co., Ltd. with a number average particle size of 200 nm): A-3), the rest are all EM-5 was obtained in the same manner as in Reference Example 2.

<Reference example 6> Emulsion (EM-6) containing metal oxide particles (a) with acrylic resin (D) on the surface (AD)

Except for the metal oxide particles (a) which use tin-antimony oxide particles (T-1 series (Mitsubishi Materials Electronic Chemicals Co., Ltd. number average particle size 60nm): A-4), the rest are in accordance with the reference In Example 2, EM-6 was obtained in the same manner.

<Reference example 7> Emulsion (EM-7) containing metal oxide particles (a) with acrylic resin (D) on the surface (AD)

Except that the metal oxide particles (a) use Zr-containing "NANOUSE (registered trademark)" ZR (manufactured by Nissan Chemical Industry Co., Ltd. with a number average particle size of 90 nm): A-5, the rest are in accordance with Reference Example 2 Obtain EM-7 in the same way.

<Reference example 8> Emulsion (EM-8) containing metal oxide particles (a) with acrylic resin (D) on the surface (AD)

Except for the metal oxide particles (a) which use the "SNOWTEX (registered trademark)" colloidal silica slurry containing Si element (manufactured by Nissan Chemical Industry Co., Ltd., the number average particle size is 80nm): A-6, the rest are all EM-8 was obtained in the same way as in Reference Example 2.

<Reference Example 9> Emulsion (EM-9) containing metal oxide particles (a) with acrylic resin (D) on the surface (AD)

A common acrylic resin reaction tank equipped with a stirrer, a thermometer, and a reflux cooling tube is filled with 100 parts by weight of isopropanol as a solvent, heated and stirred, and kept at 100°C.

Among them, dripped over 3 hours: (meth)acrylate (d'-1) n=19 eicosanyl methacrylate 40 parts by weight, (meth)acrylate (d'-2) 40 parts by weight of 2-ring isobornyl methacrylate and (meth)acrylates with other hydroxyl groups A mixture of 10 parts by weight of 2-hydroxyethyl acrylate (d'-3) and 10 parts by weight of 2,2,2-trifluoroethyl acrylate (d'-4). Then, after the dropping is completed, heating is performed at 100°C for 1 hour, and then an additional catalyst mixture composed of 1 part by weight of 2-ethylhexanoic acid-tert-butyl peroxide is filled. Then, after heating at 100 degreeC for 3 hours, it cooled and obtained the acrylic resin (D-2).

Except that acrylic resin (D-2) was used for the acrylic resin, EM-9 was obtained in the same manner as in Reference Example 2.

<Reference example 10> Preparation of acrylic resin (D-3)

In a nitrogen environment and at room temperature (25°C), fill container 1 with: 100 parts by weight of water, 1 part by weight of polyethylene glycol monomethacrylate (ethylene oxide repeating unit 16), and ammonium persulfate 0.5 part by weight was heated to 70°C to dissolve, and a 70°C solution 1 was obtained. Next, at normal temperature (25° C.), the following raw materials were added to the container 2 in the following ratio, and stirred to obtain a solution 2.

Then, 50 parts by weight of water was added to 100 parts by weight of solution 2 to obtain solution 3. Under a nitrogen atmosphere, the solution 1 was moved into the reactor, and the solution 3 was continuously dropped into the solution 1 over 3 hours while maintaining the temperature of the solution in the reactor at 70°C. After the dripping is over, it is stirred at 85 degrees for 2 hours, then cooled to 25 degrees, and neutralized with ammonia to obtain an acrylic resin (D-3) emulsion.

<Reference Example 11> Emulsion (EM-10) containing metal oxide particles (a) with acrylic resin (D) on the surface (AD)

Except that the addition amount ratio (weight ratio) of the metal oxide particles (a) and the acrylic resin (D-1) is changed to (A)/(D-1)=20/80, the rest are in accordance with the reference example 1 Similarly, EM-10 was obtained.

<Reference example 12> Emulsion (EM-11) containing metal oxide particles (a) with acrylic resin (D) on the surface (AD)

Except that the addition amount ratio (weight ratio) of metal oxide particles (a) and acrylic resin (D-1) is changed to (A)/(D-1)=80/20, the rest are in accordance with the reference example 1 Similarly, EM-11 was obtained.

<Reference Example 13> Emulsion (EM-12) containing a composition (AD) of metal oxide particles (a) with acrylic resin (D) on the surface

Except that the metal oxide particles (a) use Zr-containing "NANOUSE (registered trademark)" ZR ((number average particle size 20nm made by Nissan Chemical Industry Co., Ltd.): A-7), the rest are in accordance with the reference Example 2 obtained EM-12 in the same way.

<Reference Example 14> Conductive compound B-1

Containing 20.8 parts by weight of polystyrene sulfonic acid which is an acidic polymer compound To 1887 parts by weight of the aqueous solution, 49 parts by weight of 1% by weight iron (III) sulfate aqueous solution, 8.8 parts by weight of 3,4-dioxyethylenethiophene, which is a thiophene compound, and 117 parts by weight of 10.9% by weight peroxydisulfuric acid aqueous solution were added . The mixture was stirred at 18°C for 23 hours. Then, 154 parts by weight of cation exchange resin and 232 parts by weight of anion exchange resin were added to the mixture, and after stirring for 2 hours, the ion exchange resin was filtered to obtain poly(3,4-dioxoethylenethiophene) Water dispersion B-1 (solid content concentration 1.3% by weight) of a mixture with polystyrene sulfonic acid.

<Reference Example 15> Conductive compound B-2

The polystyrene sulfonate ammonium salt (weight average molecular weight: 75,000) was diluted in water to obtain an aqueous solution of polystyrene sulfonate ammonium salt B-2 (solid content concentration: 5 wt%).

<Example 1>

First, the coating composition 1 was prepared as follows.

<Coating composition>

In an aqueous solvent, the following emulsion was mixed at the ratio described in the table to obtain a coating composition 1.

‧Emulsion (EM-1) containing metal oxide particles (a) with acrylic resin (D) on the surface (AD): 100 parts by weight

‧Melamine-based compounds ("BECKAMINE" (registered trademark) APM manufactured by DIC Corporation) (C-1): 20 parts by weight

‧Conductive compound (B-1): 25 parts by weight (solid part weight)

<Laminated polyester film>

Next, fully apply PET particles (with an ultimate viscosity of 0.63dl/g) that do not contain particles. After vacuum drying, it is supplied to an extruder, melted at 285℃, and then extruded into a sheet form using a T-shaped spinneret. Using electrostatic casting method, it is wound on a mirror casting with a surface temperature of 25℃ On the drum while allowing to cool and solidify. This unstretched film was heated to 90°C, and then stretched 3.4 times in the longitudinal direction to form a uniaxially stretched film (B film).

Next, the coating composition 1 was coated on the corona discharge treatment surface of the uniaxially stretched film using a bar coater. The two ends in the width direction of the uniaxially stretched film coated with the coating composition are held by a clamp and guided to the preheating zone. After the ambient temperature is set to 75°C, a radiant heater is used to set the ambient temperature The temperature is 110°C, and then the ambient temperature is set to 90°C to dry the coating composition to form a layer (X). Then, it was continuously stretched 3.5 times in the width direction in a 120°C heating zone (extension zone), and then heat-treated for 20 seconds in a 230°C heat treatment zone (heat-fixing zone) to obtain a laminated polyester film with complete crystal alignment. The cross section of the obtained laminated polyester film was observed using a transmission electron microscope (TEM), and the measured PET film thickness was 50 μm and the thickness of the layer (X) was 1000 nm. The characteristics of the obtained laminated polyester film are shown in the table. The initial surface specific resistance, the rate of change after one month, transparency, scratch resistance, and interference spots are all excellent.

<Example 2>

The resin film was obtained in the same manner as in Example 1 except that the coating composition in the coating liquid was changed as follows. The characteristics of the obtained resin film are shown in the table.

<Coating composition>

In the water-based solvent, the following emulsion was mixed at the ratio described in the table to obtain coating composition 2.

‧Emulsion (EM-2) containing metal oxide particles (a) with acrylic resin (D) on the surface (AD): 100 parts by weight

‧Melamine-based compounds ("BECKAMINE" (registered trademark) APM manufactured by DIC Corporation) (C-1): 20 parts by weight

‧Conductive compound (B-1): 25 parts by weight (solid part weight)

<Example 3>

The resin film was obtained in the same manner as in Example 1 except that the coating composition in the coating liquid was changed as follows. The characteristics of the obtained resin film are shown in the table.

<Coating composition>

In an aqueous solvent, the following emulsion was mixed at the ratio described in the table to obtain a coating composition 3.

‧Emulsion (EM-3) containing metal oxide particles (a) with acrylic resin (D) on the surface (AD): 100 parts by weight

‧Melamine-based compounds ("BECKAMINE" (registered trademark) APM manufactured by DIC Corporation) (C-1): 20 parts by weight

‧Conductive compound (B-1): 25 parts by weight (solid part weight)

<Example 4>

The resin film was obtained in the same manner as in Example 1 except that the coating composition in the coating liquid was changed as follows. The characteristics of the obtained resin film are shown in the table.

<Coating composition>

In an aqueous solvent, the following emulsion was mixed at the ratio described in the table to obtain a coating composition 4.

‧Emulsion (EM-4) containing metal oxide particles (a) with acrylic resin (D) on the surface (AD): 100 parts by weight

‧Melamine-based compounds ("BECKAMINE" (registered trademark) APM manufactured by DIC Corporation) (C-1): 20 parts by weight

‧Conductive compound (B-1): 25 parts by weight (solid part weight)

<Example 5>

The resin film was obtained in the same manner as in Example 1 except that the coating composition in the coating liquid was changed as follows. The characteristics of the obtained resin film are shown in the table.

<Coating composition>

In the water-based solvent, the following emulsion was mixed at the ratio described in the table to obtain coating composition 5.

‧Emulsion (EM-5) containing metal oxide particles (a) with acrylic resin (D) on the surface (AD): 100 parts by weight

‧Melamine-based compounds ("BECKAMINE" (registered trademark) APM manufactured by DIC Corporation) (C-1): 20 parts by weight

‧Conductive compound (B-1): 25 parts by weight (solid part weight)

<Example 6>

The resin film was obtained in the same manner as in Example 1 except that the coating composition in the coating liquid was changed as follows. The characteristics of the obtained resin film are shown in the table.

<Coating composition>

In an aqueous solvent, the following emulsion was mixed in the ratio described in the table to obtain a coating composition 6.

‧Emulsion (EM-6) containing metal oxide particles (a) with acrylic resin (D) on the surface (AD): 100 parts by weight

‧Melamine-based compounds ("BECKAMINE" (registered trademark) APM manufactured by DIC Corporation) (C-1): 20 parts by weight

‧Conductive compound (B-1): 25 parts by weight (solid part weight)

<Example 7>

The resin film was obtained in the same manner as in Example 1 except that the coating composition in the coating liquid was changed as follows. The characteristics of the obtained resin film are shown in the table.

<Coating composition>

In the water-based solvent, the following emulsion was mixed at the ratio described in the table to obtain coating composition 7.

‧Emulsion (EM-7) containing metal oxide particles (a) with acrylic resin (D) on the surface (AD): 100 parts by weight

‧Melamine-based compounds ("BECKAMINE" (registered trademark) APM manufactured by DIC Corporation) (C-1): 20 parts by weight

‧Conductive compound (B-1): 25 parts by weight (solid part weight)

<Example 8>

The resin film was obtained in the same manner as in Example 1 except that the coating composition in the coating liquid was changed as follows. The characteristics of the obtained resin film are shown in the table.

<Coating composition>

In an aqueous solvent, the following emulsion was mixed at the ratio described in the table to obtain a coating composition 8.

‧Emulsion (EM-8) containing metal oxide particles (a) with acrylic resin (D) on the surface (AD): 100 parts by weight

‧Melamine-based compounds ("BECKAMINE" (registered trademark) APM manufactured by DIC Corporation) (C-1): 20 parts by weight

‧Conductive compound (B-1): 25 parts by weight (solid part weight)

<Example 9>

The resin film was obtained in the same manner as in Example 1 except that the coating composition in the coating liquid was changed as follows. The characteristics of the obtained resin film are shown in the table.

<Coating composition>

In the water-based solvent, the following emulsion was mixed at the ratio described in the table to obtain coating composition 9.

‧Emulsion (EM-2) containing metal oxide particles (a) with acrylic resin (D) on the surface (AD): 100 parts by weight

‧Melamine-based compound ("BECKAMINE" (registered trademark) APM manufactured by DIC (Stock)) (C-1): 40 parts by weight

‧Conductive compound (B-1): 25 parts by weight (solid part weight)

<Example 10>

The resin film was obtained in the same manner as in Example 1 except that the coating composition in the coating liquid was changed as follows. The characteristics of the obtained resin film are shown in the table.

<Coating composition>

In an aqueous solvent, the following emulsion was mixed at the ratio described in the table to obtain a coating composition 10.

‧Emulsion (EM-2) containing metal oxide particles (a) with acrylic resin (D) on the surface (AD): 100 parts by weight

‧Isocyanate compound (C-2): "ELASTRON" (registered trademark) E-37 (solid content 28%, solvent: water) manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.: 20 parts by weight

‧Conductive compound (B-1): 25 parts by weight (solid part weight)

<Example 11>

The resin film was obtained in the same manner as in Example 1 except that the coating composition in the coating liquid was changed as follows. The characteristics of the obtained resin film are shown in the table.

<Coating composition>

In an aqueous solvent, the following emulsion was mixed at the ratio described in the table to obtain a coating composition 11.

‧Emulsion (EM-2) containing metal oxide particles (a) with acrylic resin (D) on the surface (AD): 100 parts by weight

‧Carbondiimide compounds ("CARBODILITE" (registered trademark) V-04B manufactured by Nisshinbo) (C-3): 20 parts by weight

‧Conductive compound (B-1): 25 parts by weight (solid part weight)

<Example 12>

The resin film was obtained in the same manner as in Example 1 except that the coating composition in the coating liquid was changed as follows. The characteristics of the obtained resin film are shown in the table.

<Coating composition>

In an aqueous solvent, the following emulsion was mixed at the ratio described in the table to obtain a coating composition 12.

‧Emulsion (EM-9) containing metal oxide particles (a) with acrylic resin (D) on the surface (AD): 100 parts by weight

‧Melamine-based compounds (“BECKAMINE” (registered trademark) APM manufactured by DIC (Stock)): 20 parts by weight

‧Conductive compound (B-1): 25 parts by weight (solid part weight)

<Example 13>

The resin film was obtained in the same manner as in Example 2 except that the thickness of the layer (X) was changed to 80 nm. The characteristics of the obtained resin film are shown in the table.

<Example 14>

The resin film was obtained in the same manner as in Example 1 except that the coating composition in the coating liquid was changed as follows. The characteristics of the obtained resin film are shown in the table.

<Coating composition>

In the water-based solvent, the following emulsion was mixed at the ratio described in the table to obtain coating composition 2.

‧Emulsion (EM-2) containing metal oxide particles (a) with acrylic resin (D) on the surface (AD): 100 parts by weight

‧Melamine-based compounds ("BECKAMINE" (registered trademark) APM manufactured by DIC (Stock)) (C-1): 10 parts by weight

‧Carbon diimide compounds ("CARBODILITE" (registered trademark) V-04B manufactured by Nisshinbo Co., Ltd.) (C-3): 10 parts by weight

‧Conductive compound (B-1): 25 parts by weight (solid part weight)

<Example 15>

The resin film was obtained in the same manner as in Example 1 except that the coating composition in the coating liquid was changed as follows. The characteristics of the obtained resin film are shown in the table.

<Coating composition>

In the water-based solvent, the following emulsion was mixed at the ratio described in the table to obtain coating composition 2.

‧Emulsion (EM-2) containing metal oxide particles (a) with acrylic resin (D) on the surface (AD): 100 parts by weight

‧Isocyanate compound (C-2): "ELASTRON" (registered trademark) E-37 (solid content 28%, solvent: water) manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.: 10 parts by weight

‧Carbon diimide compounds ("CARBODILITE" (registered trademark) V-04B manufactured by Nisshinbo Co., Ltd.) (C-3): 10 parts by weight

‧Conductive compound (B-1): 25 parts by weight (solid part weight)

<Example 16>

The resin film was obtained in the same manner as in Example 1 except that the coating composition in the coating liquid was changed as follows. The characteristics of the obtained resin film are shown in the table.

<Coating composition>

In the water-based solvent, the following emulsion was mixed at the ratio described in the table to obtain coating composition 2.

‧Emulsion (EM-2) containing metal oxide particles (a) with acrylic resin (D) on the surface (AD): 100 parts by weight

‧Isocyanate compound (C-2): "ELASTRON" (registered trademark) E-37 (solid content 28%, solvent: water) manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.: 5 parts by weight

‧Carbondiimide compounds ("CARBODILITE" (registered trademark) V-04B manufactured by Nisshinbo Co., Ltd.) (C-3): 15 parts by weight

‧Conductive compound (B-1): 25 parts by weight (solid part weight)

<Example 17>

In the water-based solvent, the following emulsion was mixed at the ratio described in the table to obtain coating composition 2.

‧Emulsion (EM-2) containing metal oxide particles (a) with acrylic resin (D) on the surface (AD): 100 parts by weight

‧Melamine-based compounds ("BECKAMINE" (registered trademark) APM manufactured by DIC Corporation) (C-1): 20 parts by weight

‧Conductive compound (B-2): 25 parts by weight (solid part weight)

<Example 18>

In the water-based solvent, the following emulsion was mixed at the ratio described in the table to obtain coating composition 2.

‧Emulsion (EM-3) containing metal oxide particles (a) with acrylic resin (D) on the surface (AD): 100 parts by weight

‧Melamine-based compounds ("BECKAMINE" (registered trademark) APM manufactured by DIC Corporation) (C-1): 20 parts by weight

‧Conductive compound (B-2): 25 parts by weight (solid part weight)

<Example 19>

In the water-based solvent, the following emulsion was mixed at the ratio described in the table to obtain coating composition 2.

‧Emulsion (EM-1) containing metal oxide particles (a) with acrylic resin (D) on the surface (AD): 100 parts by weight

‧Melamine-based compounds ("BECKAMINE" (registered trademark) APM manufactured by DIC Corporation) (C-1): 20 parts by weight

‧Conductive compound (B-2): 25 parts by weight (solid part weight)

<Comparative Example 1>

The resin film was obtained in the same manner as in Example 1 except that the coating composition in the coating liquid was changed as follows. The characteristics of the obtained resin film are shown in the table.

<Coating composition>

In an aqueous solvent, the following emulsion was mixed at the ratio described in the table to obtain a coating composition 13.

‧Emulsion (EM-2) containing metal oxide particles (a) with acrylic resin (D) on the surface (AD): 100 parts by weight

‧Melamine-based compounds ("BECKAMINE" (registered trademark) APM manufactured by DIC Corporation) (C-1): 20 parts by weight

<Comparative Example 2>

The resin film was obtained in the same manner as in Example 1 except that the coating composition in the coating liquid was changed as follows. The characteristics of the obtained resin film are shown in the table.

<Coating composition>

In an aqueous solvent, the following emulsion was mixed in the ratio described in the table to obtain a coating composition 14.

‧Acrylic resin (D-3): 100 parts by weight

‧Melamine-based compounds ("BECKAMINE" (registered trademark) APM manufactured by DIC Corporation) (C-1): 20 parts by weight

‧Conductive compound (B-1): 25 parts by weight (solid part weight)

<Comparative Example 3>

The resin film was obtained in the same manner as in Example 1 except that the coating composition in the coating liquid was changed as follows. The characteristics of the obtained resin film are shown in the table.

<Coating composition>

In an aqueous solvent, the following emulsion was mixed at the ratio described in the table to obtain a coating composition 15.

‧Emulsion (EM-10) containing metal oxide particles (a) with acrylic resin (D) on the surface (AD): 100 parts by weight

‧Melamine-based compounds ("BECKAMINE" (registered trademark) APM manufactured by DIC Corporation) (C-1): 20 parts by weight

‧Conductive compound (B-1): 25 parts by weight (solid part weight)

<Comparative Example 4>

The resin film was obtained in the same manner as in Example 1 except that the coating composition in the coating liquid was changed as follows. The characteristics of the obtained resin film are shown in the table.

<Coating composition>

In an aqueous solvent, the following emulsion was mixed in the ratio described in the table to obtain a coating composition 16.

‧Emulsion (EM-11) containing metal oxide particles (a) with acrylic resin (D) on the surface (AD): 100 parts by weight

‧Melamine-based compounds ("BECKAMINE" (registered trademark) APM manufactured by DIC Corporation) (C-1): 20 parts by weight

‧Conductive compound (B-1): 25 parts by weight (solid part weight)

<Comparative Example 5>

The resin film was obtained in the same manner as in Example 1 except that the coating composition in the coating liquid was changed as follows. The characteristics of the obtained resin film are shown in the table.

<Coating composition>

In an aqueous solvent, the following emulsion was mixed in the ratio described in the table to obtain a coating composition 17.

‧Emulsion (EM-2) containing metal oxide particles (a) with acrylic resin (D) on the surface (AD): 100 parts by weight

‧Melamine-based compounds ("BECKAMINE" (registered trademark) APM manufactured by DIC Corporation) (C-1): 20 parts by weight

‧Conductive compound (B-1): 10 parts by weight (solid part weight)

<Comparative Example 6>

The resin film was obtained in the same manner as in Example 1 except that the coating composition in the coating liquid was changed as follows. The characteristics of the obtained resin film are shown in the table.

<Coating composition>

In an aqueous solvent, the following emulsion was mixed at the ratio described in the table to obtain a coating composition 18.

‧Emulsion (EM-12) containing metal oxide particles (a) with acrylic resin (D) on the surface (AD): 100 parts by weight

‧Melamine-based compounds ("BECKAMINE" (registered trademark) APM manufactured by DIC Corporation) (C-1): 20 parts by weight

‧Conductive compound (B-1): 25 parts by weight (solid part weight)

[Table 1]

[Table 2]

[table 3]

In addition, in the table, whether the relevant insulating phase (A) and conductive phase (B) are present or not, "Y" means "Yes" and "N" means "None". Also, in the table, the E system represents an exponential function, for example, "1.0E+07" represents "1.0×10 ⁷ ".

(Industrial availability)

The present invention relates to a combination of a resin film having antistatic properties and scratch resistance, and the antistatic properties have little change in response to the environment. It is quite suitable for the processing of various industrial products Plastic films used (especially hard-coated films used for display applications), hard-coated films used for molding and decoration applications, and base materials for metal laminates.

Claims (10)

A resin film with at least one surface provided with a conductivity measurement mode (conductive AFM) using AFM (Atomic Force Microscope), the measured insulating phase (A) and conductive phase (B), When the surface with the insulating phase (A) and the conductive phase (B) is set as the surface α, the area occupied by the insulating phase (A) in the surface α is 40% to 80%, and the surface resistivity of the surface α is 1.0×10 ¹⁰ Ω/□ or less. The resin film of claim 1, wherein the average area diameter of the insulating phase (A) in the surface α is 50 nm or more and 200 nm or less. The requested item resin film 1 or 2, wherein said surface α of the insulating phase (A) electrically conductive I _A, and the conductive phase (B) conductive I _B ratio I _A / I _B, lines Above 100 and below 100,000. The resin film according to any one of claims 1 to 3, wherein the haze change of the surface α before and after the wiping treatment is 3.0% or less. The resin film according to any one of claims 1 to 4, wherein, in the surface α, the elastic modulus (GA) of the insulating phase ( _A ) is 2000 MPa or more and 50000 MPa or less. The requested item 1 to 5 of a resin film, wherein the α surface, the insulating phase (A) elastic modulus (G _A), the conductive phase (B) elastic modulus (G _B) of The ratio G _A /G _B is 4 or more and 20 or less. The resin film according to any one of claims 1 to 6, which is a laminate of two or more layers including a supporting substrate and a layer (X) formed on the surface thereof. A resin film according to any one of claims 1 to 7, wherein the insulating phase (A) contains metal oxide particles (a), and the metal oxide particles (a) contain Si, Al, Ti, At least one metal element is selected from the group consisting of Zr, Se, and Fe. The resin film according to any one of claims 1 to 8, wherein the conductive phase (B) contains: a polythiophene-based conductive compound (b), epoxy resin, melamine resin,

At least one crosslinking agent (c) is selected from the oxazoline compound, carbonyldiimide compound, and isocyanate compound. A method for manufacturing a resin film, which is the method for manufacturing a resin film according to any one of claims 1 to 9, comprising: coating the coating composition (x) on at least one side of the polyester film before crystallization is completed , Perform the steps of stretching and heat treatment in at least one direction; the coating composition (x) contains: metal oxide particles (a), conductive components (b), and epoxy resin, melamine resin,

At least one crosslinking agent (c) is selected from the oxazoline compound, carbonyldiimide compound, and isocyanate compound.

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