JP7419817B2 - Resin film and its manufacturing method - Google Patents

Description

The present invention relates to a resin film and a method for manufacturing the same.

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 used in many applications such as magnetic recording materials and packaging materials. Widely used in various applications. Particularly in recent years, in addition to carrier films used in the processing of various industrial products, various optical applications including display materials such as touch panels, liquid crystal display panels (LCD), plasma display panels (PDP), and organic electroluminescence (organic EL) have been developed. The quality required of polyester films, such as those used in industrial applications, is increasing. Against this background, there is a demand for both "antistatic properties" and "scratch resistance" for the purpose of suppressing scratches and foreign substances in the manufacturing and processing processes of polyester films.

Antistatic property is imparted for the purpose of suppressing foreign matter defects caused by dust adhesion due to charging. For example, Patent Document 1 describes a method in which an antistatic agent is added to a polyester resin and applied thereto, and Patent Document 2 describes a method in which a styrene sulfonic acid copolymer is applied. As a practical issue, it is often a problem that the antistatic property changes due to changes in the environment such as humidity and temperature during use and the elapsed time from manufacture.

On the other hand, scratch resistance is provided for the purpose of suppressing surface abrasion due to contact with conveyor rolls during processing or slippage. For example, a hard coat film is used, which is a laminated layer (hard coat layer) made of ultraviolet (UV) curable resin. Processability that allows for clean punching is required. If workability is poor, cracks may occur at the edges, impairing the design, or fragments may lead to defects.

In response to such demands, Patent Document 3 proposes a film in which a conductive material is mixed in a hard coat layer, and Patent Document 4 proposes a laminated film in which the upper surface of the antistatic layer is further coated with a hard coat layer.

Japanese Unexamined Patent Publication No. 61-204240 Japanese Unexamined Patent Publication No. 7-101016 JP2011-033658A JP2008-176317A

However, for example, the laminated films having antistatic layers disclosed in Patent Documents 1 and 2 lack the effect of suppressing scratches during processing steps. On the other hand, the techniques described in Patent Documents 3 and 4 make it possible to suppress scratches. However, in Patent Document 3, it is not possible to sufficiently achieve both scratch resistance and antistatic property. Furthermore, in the technique of Patent Document 4, the antistatic performance is insufficient in the process after hard coating.

Therefore, it is an object of the present invention to provide a technology that can eliminate the above-mentioned drawbacks and stably mass-produce a resin film that can achieve both antistatic properties and scratch resistance.

In order to solve the above problems, the resin film of the present invention has the following configuration.
(1) At least one surface has an insulating phase (A) and a conductive phase (B) measured in a conductive measurement mode (conductive AFM) of an Atomic Force Microscope (AFM), and When a surface having a phase (A) and a conductive phase (B) is defined as a surface α, the area occupied by the insulating phase (A) on the surface α is 40% or more and 80% or less, and the surface resistivity of the surface α is is 10 ¹⁰ Ω/□ or less.
(2) The resin film according to (1), wherein the average domain diameter of the insulating phase (A) on the surface α is 50 nm or more and 200 nm or less.
(3) The ratio I A /I B of the conductivity I _A of the insulating phase (A) to the conductivity I _B of the conductive phase ( _B ) on the surface _α is 100 or more and 100,000 or less (1) or ( 2) The resin film according to item 2).
(4) The resin film according to any one of (1) to (3), wherein the haze change before and after the abrasion treatment on the surface α is 3.0% or less.
(5) The resin film according to any one of (1) to (4), wherein the elastic modulus (G _A ) of the insulating phase (A) on the surface α is 2000 MPa or more and 50000 MPa or less.
(6) The ratio of the elastic modulus (G A ) of the insulating phase ( _A ) to the elastic modulus (G B ) of the conductive phase ( _B ) on the surface α, G _A /G _B is 4 or more and 20 or less (1 ) to (5).
(7) The resin film according to any one of (1) to (6), which is a laminate of two or more layers including a supporting base material and a layer (X) formed on the surface thereof.
(8) From (1), wherein the insulating phase (A) contains metal oxide particles (a) containing at least one metal element selected from the group consisting of Si, Al, Ti, Zr, Se, and Fe. (9) The conductive phase (B) is a polythiophene-based conductive compound (b) and at least one selected from epoxy resins, melamine resins, oxazoline compounds, carbodiimide compounds, and isocyanate compounds. The resin film according to any one of (1) to (8), containing a type of crosslinking agent (c).
(10) The method for producing a resin film according to any one of (1) to (9), in which the coating composition (x) is applied to at least one side of the polyester film before crystal orientation is completed, and then The coating composition (x) includes a step of performing stretching treatment and heat treatment in at least one direction, and the coating composition (x) contains metal oxide particles (a), a conductive component (b), an epoxy resin, a melamine resin, an oxazoline compound, a carbodiimide compound, A method for producing a resin film containing at least one crosslinking agent (c) selected from isocyanate compounds.

The resin film of the present invention has both antistatic properties and scratch resistance, has little change in antistatic properties depending on the environment (that is, has excellent stability), and reduces the manufacturing burden by shortening the number of steps in the manufacturing process. You can.

FIG. 2 is a schematic diagram showing the conductivity distribution obtained by measuring the surface of the resin film of the present invention in conductivity measurement mode (conductive AFM) of AFM (Atomic Force Microscope). (In actual measurements, a 1 μm x 1 μm conductive image is divided into 40 vertical and horizontal regions, and divided into 1600 regions of 25 nm x 25 nm. However, in the schematic diagram, a 1 μm x 1 μm conductive image is divided into 20 vertical and horizontal regions. (It shows the divided parts.)

Hereinafter, the resin film of the present invention will be explained in detail. The resin film of the present invention has at least one surface having an insulating phase (A) and a conductive phase (B) measured by a conductive measurement mode (conductive AFM) of an Atomic Force Microscope (AFM). However, when the surface having the insulating phase (A) and the conductive phase (B) is defined as surface α, the area occupied by the insulating phase (A) on the surface α is 40% or more and 80% or less, and the laminated film It is necessary that the surface resistivity is 1×10 ¹⁰ Ω/□ or less.

First, FIG. 1 shows a schematic diagram of the conductivity distribution measured by 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 needs to have two domains with different physical properties on at least one surface. Specifically, when the surface is measured by the conductive AFM method, domains with relatively high conductivity (hereinafter referred to as conductive phase (B)) and domains with relatively low conductivity (hereinafter referred to as insulating phase (A)) are identified. ) must exist. The details will be described later, but the image obtained by conductive AFM measurement was binarized using "ScionImage" (maximum value: 10 nA, minimum value: 0 pA, threshold value 180 (black is 0, white is 255, black to white is A conductive image was created by setting the area where 10 nA or more flows as 255 (white) and the area of 0 pA as 0 (black) on a gray scale expressed in 256 steps, and in the obtained conductive image, the gray scale was 180. A conductive image is obtained by color-coding a portion with a high current value represented by the above color tones as white, and a portion having a low current value represented by a gray scale of less than 180 black. The resulting conductive image, 1 μm x 1 μm, is divided into 40 vertical and horizontal sections, and divided into 1,600 regions of 25 nm x 25 nm. Among the 1,600 regions, one region in which all black is solid is called the insulating phase (A). , the solid white one is the conductive phase (B). In solving the problems of the present invention, the inventors investigated and found that materials used to impart antistatic properties are often composed of a collection of polymers with low hardness or materials with low molecular weight. We confirmed that its properties change easily in response to external stimuli such as pressure, temperature, and humidity. In contrast, by providing an insulating phase (A), which is a domain that does not substantially contain an antistatic component, on the film surface, it is possible to achieve both antistatic properties and scratch resistance, and to stabilize the antistatic properties. I found out what I can achieve.

Further, on the surface α, there is a necessary ratio of the area occupied by the insulating phase (A) to the entire surface α. Specifically, the area occupied by the insulating phase (A) needs to 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, making it impractical. On the other hand, if the area occupied by the entire surface α exceeds 80%, it is not preferable because the antistatic performance is insufficient. Regarding the design of the conductive phase (B) and the insulating phase (A), control the compatibility of the resin material, adjust the coating drying conditions, and when using filler materials, adjust the blending amount and particle size of the filler materials. It can be adjusted. Note that specific methods for measuring each area, preferred coating compositions, and manufacturing methods will be described later. Note that a particularly preferable range of the area occupied by the entire surface α of the insulating phase (A) is 40% or more and 60% or less.

Next, a description will be given of changes in haze before and after subjecting the surface α of the resin film of the present invention to the abrasion treatment. Here, the haze refers to a value defined in JIS K 7136 (2000), and the haze of a film is treated as an index that mainly indicates the transparency of the film. When scratches occur on the surface of a film due to abrasion treatment, transparency decreases. Therefore, comparing the haze values before and after the scratching process corresponds to evaluating the amount of scratches on the surface caused by the scratching process.

The surface α of the resin film of the present invention preferably has a haze change of 3.0% or less before and after the abrasion treatment under the conditions described below. If it exceeds 3.0%, it corresponds to insufficient hardness of the coating film, insufficient film forming properties, or insufficient formation of the insulating phase (A) described below. As a result, not only the scratch resistance is insufficient, but also the antistatic property becomes unstable. In particular, the antistatic property tends to fluctuate under conditions of oxygen exposure, and sufficient stability may not be obtained. Note that a specific method of abrasion treatment and a method of measuring haze will be described later. It is more preferably 2.5% or less, and even more preferably 1.9% or less.

Further, the surface α of the resin film of the present invention needs to have a surface resistivity of 1×10 ¹⁰ Ω/□ or less. The surface resistivity is a value determined by the measurement method described below, and is an index representing the average conductivity in a more macroscopic range of the resin film surface compared to the measurement by the conductivity measurement mode of the AFM described above. If the surface resistivity exceeds 1× ¹⁰ Ω/□, the ratio of the insulating phase (A) mentioned above may be too large, or the conductive phase (B) may not have sufficient antistatic properties. Performance cannot be obtained. A method for measuring surface resistivity will be described later. The surface resistivity is preferably 1×10 ⁹ Ω/□ or less, particularly preferably 1×10 ⁷ Ω/□ or less. On the other hand, the lower limit is not particularly limited, but is preferably 1×10 ⁴ Ω/□ or more in a practical configuration from the viewpoint of film-forming properties and cost.

[Resin film and laminated resin film]
The resin constituting the resin film in the present invention is not particularly limited, and examples thereof include known acrylic resins, polyester resins, urethane resins, melamine resins, and epoxy resins. In the present invention, acrylic resins and melamine resins are preferred from the viewpoint of stability when produced by the preferred manufacturing method described below.

The resin film in the present invention may have a surface α that satisfies the above conditions on at least one surface, and may be a single layer film or a laminated film. It may have a layer formed on at least one surface or both surfaces of the supporting base material.

Here, the "layer" in the present invention refers to a boundary in which the composition of constituent elements, the shape of inclusions such as particles, and the physical properties in the thickness direction are discontinuous with respect to the adjacent parts in the thickness direction from the surface of the laminate. Refers to a region with a finite thickness that is distinguished by having a surface. More specifically, the laminate is examined in the thickness direction from the surface using various composition/element analyzers (FT-IR, XPS, XRF, EDAX, SIMS, EPMA, EELS, etc.), electron microscopes (transmission type, scanning type), or It refers to a region that is distinguished by the discontinuous boundary surface and has a finite thickness when a cross section is observed with an optical microscope.

[Layer (X)]
The resin film of the present invention preferably has a layer (X) designed from the viewpoint of antistatic properties and scratch resistance on at least one surface of the supporting base material, and the layer (X) preferably has a layer (X) on at least one surface of the supporting base material. It is preferable to have α. As the resin constituting the layer (X), the resins listed above as the resin constituting the resin film can be preferably used. The method for forming the layer (X) is not particularly limited as long as the above-mentioned conditions can be met, but it is preferably formed using a coating composition. A film may be created by applying the coating composition described below during the film formation of the support base material, or after the film formation of the support base material, the paint composition is applied to the support base material, dried, and rolled up. You can.

For example, when layer (X) is formed by coating, the thickness of layer (X) (coating thickness after drying) is preferably 10 to 2000 nm, more preferably 40 to 1000 nm, and still more preferably 80 to 800 nm. It is preferable that the thickness is from 10 nm to 2000 nm because the desired functions to be imparted by the layer (X), ie, antistatic properties, scratch resistance, and coating film quality, can be obtained.

[Conductivity measurement using AFM]
The resin film of the present invention has a conductive phase (B) and an insulating phase (A) observed on at least one surface when measured by conductive AFM. Here, we will provide an overview of conductivity measurement using an atomic force microscope. Atomic force microscopy is a method that uses a cantilever with an atomic-level sharp tip to measure irregularities by scanning the surface shape. - By applying a voltage between samples, it is possible to detect and map the generation of weak currents on the film surface. Such measurements can be performed in conductive measurement mode or conductive AFM (Conductive AFM).
AFM: called c-AFM). In conductive AFM measurements, it is possible to detect minute currents (tunnel currents) that seep beyond the insulating air layer, and it is possible to detect minute differences in conductivity in a minute area directly under the cantilever (conductivity on the film surface). ) can be detected efficiently. Details and measurement methods will be described later.

In the resin film of the present invention, there is a preferable range for the shape of the domains formed by the insulating phase (A) on the surface α. Specifically, the average domain diameter of the insulating phase (A) on the surface α is preferably 50 nm or more and 200 nm or less, particularly preferably 50 nm or more and 100 nm or less. If the average domain 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 inhibited, and as a result, sufficient antistatic properties may not be obtained. As a method for controlling the average domain diameter, when a metal oxide is used as a constituent material of the insulating phase (A) in a preferred coating composition described below, the particle diameter can be used to control the average domain diameter.

[Conductivity I B of the conductive phase ( _B ) and conductivity I _A of the insulating phase (A)]
There is a preferable numerical range for the current value (indicator of conductivity) obtained when the resin film of the present invention is measured by conductive AFM. Specifically, the ratio IB/ _IA of the conductivity _IB of the conductive phase (B) to the conductivity _IB of the insulating phase ( _A ) is preferably 100 or more and 100000 or less, and 3000 or more and 100000 or less. Particularly preferred. If the conductivity ratio I _B /I _A is less than 100, the separation structure between the insulating phase (A) and the conductive phase (B) described above will not be sufficiently formed, resulting in insufficient scratch resistance or charging. Prevention performance may become unstable. On the other hand, the upper limit is not particularly limited, but is preferably 100,000 or less. Details and measurement methods will be described later.

[Elastic modulus measurement using AFM]
In addition, the surface α of the resin film of the present invention has a preferable numerical range for the elastic modulus measured by an atomic force microscope. Specifically, the elastic modulus _GA of the insulating phase (A) is preferably 2,000 MPa or more and 50,000 MPa or less, particularly preferably 5,000 MPa or more and 20,000 MPa or less. If it is less than 2000 MPa, the above-mentioned scratch resistance may not be obtained or the stability of antistatic performance may not be obtained. On the other hand, if it exceeds 50,000 MPa, the processability of the film may be reduced, such as cracks being more likely to occur during film processing.

Furthermore, the surface α of the resin film of the present invention has a preferable range for the ratio G _A / _GB of the elastic modulus G _A of the insulating phase (A) to the elastic modulus G _B of the conductive phase (B). Specifically, G _A / _GB 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. When G _A /G _B is less than 4 or more than 20, the hardness of the resin film is biased toward the flexible side or the hard side, and it may be difficult to achieve both scratch resistance and workability.

Further, on the surface α of the resin film 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.

Here, elastic modulus measurement using an atomic force microscope is a compression test using a probe on an extremely small part, and the degree of deformation due to pressing force is measured. Therefore, a cantilever with a known spring constant is used to measure the elastic modulus of the surface α and its Spatial distribution can be measured. Specifically, elastic modulus information of each region is obtained by measuring a force curve described later in each region detected as a conductive phase (B) or an insulating phase (A) during the conductivity measurement described above. becomes possible. Although the details will be described in the Examples section, the deflection of the cantilever was determined by using the atomic force microscope shown below, bringing the probe at the tip of the cantilever into contact with the surface α, and measuring the force curve with a pressing force of 55 nN. Amounts can be measured. At this time, the spatial resolution depends on the scan range and number of scan lines of the atomic force microscope, but under realistic measurement conditions, the lower limit is approximately 50 nm. Details and measurement methods will be described later.

[Supporting base material, polyester film]
As mentioned above, the resin film of the present invention may be a single layer film or a laminated film, but a preferred form is a support base material and a layer having a surface α on at least one surface thereof (X ) is a laminated resin film. The resin used as the supporting base material is not particularly limited, but from the viewpoint of heat resistance and cost, polyester may be used. The supporting base material is preferably a layer containing polyester as the main component (hereinafter, a layer containing polyester as the main component used as the supporting base material may be referred to as a polyester film). In the present invention, the main component refers to a component that accounts for 50% by weight or more based on the entire resin constituting the layer.

In the present invention, the supporting base material preferably has a particle content of 0.1% by weight or less based on the entire supporting base material. By setting the content of particles within the above range, the internal haze can be reduced to 0.2% or less, and a resin film with excellent transparency can be obtained.

The polyester used for the support base material of the resin film of the present invention will be described below. First of all, polyester is a general term for polymers having ester bonds in the main chain, including ethylene terephthalate, propylene terephthalate, ethylene-2,6-naphthalate, butylene terephthalate, propylene-2,6-naphthalate, ethylene-α, β -Bis(2-chlorophenoxy)ethane-4,4'-dicarboxylate and the like can be preferably used.

The polyester film using the above polyester is preferably biaxially oriented. Biaxially oriented polyester film generally refers to an unstretched polyester sheet or film that is stretched approximately 2.5 to 5 times in the longitudinal direction and the width direction orthogonal to the longitudinal direction, and then heat-treated to produce crystallized It refers to a material whose orientation has been completed and which shows a biaxial orientation pattern in wide-angle X-ray diffraction. When the polyester film is biaxially oriented, it has sufficient thermal stability, particularly dimensional stability and mechanical strength, and has good flatness.

In addition, various additives such as antioxidants, heat stabilizers, weather stabilizers, ultraviolet absorbers, organic lubricants, pigments, dyes, organic or inorganic fine particles, fillers, and antistatic agents are added to the polyester film. A nucleating agent, a nucleating agent, etc. may be added to an extent that does not deteriorate the properties.

The thickness of the polyester film is not particularly limited and is appropriately selected depending on the use and type, but from the viewpoint of mechanical strength, handling properties, etc., it is usually preferably 10 to 500 μm, more preferably 15 to 250 μm. , most preferably 20 to 200 μm. Further, the polyester film may be a composite film produced by coextrusion, or a film obtained by bonding obtained films together by various methods.

[Method for manufacturing resin film]
The method for producing the resin film of the present invention will be explained below with reference to examples, but the materials, amounts used, proportions, processing details, processing procedures, etc. shown below may be changed as appropriate without departing from the spirit of the present invention. can. Therefore, the scope of the present invention should not be construed as being limited by the examples shown below.

The resin film of the present invention can be produced by applying a coating composition containing metal oxide particles (a) and a binder component onto a polyester film, and when the coating composition contains a solvent, drying the solvent. It can be obtained by forming a layer (X) thereon.

In the present invention, when the coating composition contains a solvent, it is preferable to use an aqueous solvent as the solvent (to form a water-based coating). When an aqueous solvent is used as the solvent, rapid evaporation of the solvent during the drying process can be suppressed, and a uniform composition layer can be formed, which is also excellent in terms of environmental load.

Here, the aqueous solvent refers to water, or water and alcohols such as methanol, ethanol, isopropyl alcohol, and butanol, ketones such as acetone and methyl ethyl ketone, and glycols such as ethylene glycol, diethylene glycol, and propylene glycol that are soluble in water. Refers to a mixture of organic solvents in an arbitrary ratio.

The metal oxide particles (a) and the binder component can be made into a water-based coating by including a hydrophilic group such as carboxylic acid or sulfonic acid in the metal oxide particles (a) or the binder component, or by adding an emulsifier. An example of this method is to make an emulsion using

The coating composition (x) is preferably applied to the polyester film by an in-line coating method. The in-line coating method is a method in which coating is performed within the process of manufacturing a polyester film. Specifically, it refers to a method in which coating is performed at any stage from melt extrusion of polyester resin to biaxial stretching, heat treatment, and winding. An unstretched (unoriented) polyester film in a crystalline state (A film), a uniaxially stretched (uniaxially oriented) polyester film (B film) that is then stretched in the longitudinal direction, or a biaxially stretched polyester film that is further stretched in the width direction before heat treatment. It is applied to any stretched (biaxially oriented) polyester film (C film).

In the present invention, a coating composition is applied to either the polyester film A or B before the crystal orientation is completed, and then the polyester film is stretched uniaxially or biaxially, and the solvent is removed. It is preferable to adopt a method in which heat treatment is performed at a temperature higher than the boiling point to complete the crystal orientation of the polyester film and at the same time provide the layer (X) and the surface α. According to this method, the production of the polyester film and the coating and drying of the coating composition (that is, the formation of the layer (X)) can be performed simultaneously, which is advantageous in terms of production costs. In addition, by stretching after coating, it is possible to control the agglomeration state of the metal oxide particles (a) in the layer (X), and the area and domain diameter of the insulating phase (A) can be designed to improve scratch resistance. and antistatic properties can be improved.

Among these, a method in which a coating composition is applied to a film uniaxially stretched in the longitudinal direction (B film), then stretched in the width direction, and heat-treated is excellent. Compared to the method of biaxially stretching after coating on an unstretched film, there is one less stretching step, so defects and cracks in the composition layer are less likely to occur due to stretching, and it has excellent transparency, smoothness, and antistatic properties. This is because a composition layer can be formed.

Furthermore, by providing the layer (X) using an in-line coating method, the surface alignment of the metal oxide particles (a) is promoted by applying a stretching treatment after applying the coating composition. The particles (a) are promoted to form anisotropic aggregates, and as a result, the shape of the insulating phase (A) of the layer (X) is optimized, and antistatic properties are exhibited, as well as scratch resistance and Processability and stability of antistatic performance over time and humidity changes can be improved.

In the present invention, layer (X) is preferably provided by an in-line coating method due to the various advantages mentioned above. Here, the coating composition can be applied to the polyester film by any known coating method, such as a bar coating method, a reverse coating method, a gravure coating method, a die coating method, a blade coating method, or the like.

The best method for forming layer (X) in the present invention is to apply a coating composition using an aqueous solvent onto a polyester film using an in-line coating method, dry it, and heat-treat it. Even more preferred is a method of in-line coating the coating composition on the B film after uniaxial stretching. In the method for producing a resin film of the present invention, drying can be carried out at a temperature in the range of 80 to 130° C. in order to complete the removal of the solvent from the coating composition. Further, the heat treatment can be carried out at a temperature in the range of 160 to 240° C. in order to complete the crystal orientation of the polyester film and to complete the thermal curing of the coating composition to complete the formation of layer (X). By changing the temperature and time of the above-mentioned high-temperature heat treatment, it is possible to adjust the preferred elastic modulus of the insulating phase (A) and the conductive phase (B), and it is possible to improve the scratch resistance and workability. I can do it.

Next, the method for producing a resin film of the present invention will be described using an example in which a polyethylene terephthalate (hereinafter referred to as PET) film is used as the polyester film, but the method is not limited thereto. First, PET pellets are sufficiently vacuum-dried, then supplied to an extruder, melted and extruded at about 280° C. into a sheet, and solidified by cooling to produce an unstretched (unoriented) PET film (A film). This film is stretched 2.5 to 5.0 times in the longitudinal direction using rolls heated to 80 to 120°C to obtain a uniaxially oriented PET film (B film). The coating composition of the present invention adjusted to a predetermined concentration is applied to one side of this B film.

At this time, the coated surface of the PET film may be subjected to surface treatment such as corona discharge treatment before coating. Surface treatment such as corona discharge treatment improves the wettability of the coating composition to the PET film, prevents the coating composition from being repelled, and makes it possible to form a layer (X) with a uniform coating thickness. . After coating, the ends of the PET film are held with clips and guided to a heat treatment zone (preheating zone) at 80 to 130° C. to dry the solvent of the coating composition. After drying, it is stretched 1.1 to 5.0 times in the width direction. Subsequently, it is guided to a heat treatment zone (heat fixing zone) at 160 to 240°C and heat treated for 1 to 30 seconds to complete crystal orientation.

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

In addition, in the resin film of the present invention, an intermediate layer may be provided between the layer (X) and the supporting base material, but when an intermediate layer is provided, the film on which the intermediate layer is laminated is wound up, or after In the process up to providing the layer (X) of the present invention, the film may be scratched. Therefore, in the present invention, it is preferable that the layer (X) and the supporting base material are directly laminated.

The resin film of the present invention is not limited to the structure of the supporting base material, and includes, for example, a single-layer structure consisting of only the A layer, a laminated structure of A layer/B layer, that is, a two-layer laminated structure of two types, A layer/B layer Examples include a laminated structure of /A layer, that is, a two-type three-layer laminated structure, and a laminated structure of A layer/B layer/C layer, that is, a three-type and three-layer laminated structure.

The method of laminating the supporting base material in the resin film of the present invention is not limited, and examples include a laminating method by coextrusion, a laminating method by laminating, a method by a combination of these, etc. From the viewpoint of manufacturing stability, it is preferable to employ a coextrusion method. In the case of forming a laminate, different resin compositions may be used for the purpose of imparting different functions to each layer. For example, in the case of a laminated structure of A layer/B layer/A layer, that is, a two-type, three-layer laminated structure, the B layer is made of homopolyethylene terephthalate from the viewpoint of transparency, and the A layer is made of homopolyethylene terephthalate. For this purpose, methods such as adding particles can be mentioned.

[Coating composition]
The layer (X) in the resin film of the present invention is preferably manufactured by applying a coating composition constituting the layer (X) to at least one side of a supporting substrate and then heat-treating the coating composition. Specifically, the coating composition can include metal oxide particles, an acrylic resin, a binder resin, and a conductive compound. Moreover, in addition to the above-mentioned components, various additives may be included. Preferred forms of the components contained in the coating composition will be described in detail below.

[Metal oxide particles (a)]
In the resin film of the present invention, the insulating phase (A) contains metal oxide particles (a) containing at least one metal element selected from the group consisting of Si, Al, Ti, Zr, Se, and Fe. is preferred. By containing the metal oxide particles (a), a nano-rugged structure is formed on the surface layer of the resin film, improving slipperiness and providing excellent scratch resistance. Specifically, the metal oxide particles (a) used in the resin film of the present invention include silicon dioxide (silica) (SiO ₂ ), aluminum oxide (Al ₂ O ₃ ), titanium dioxide (TiO ₂ ), and Examples include zirconium (ZrO ₂ ), selenium dioxide (SeO ₂ ), iron oxide (Fe ₂ O ₃ ) particles, and the like. One type of these may be used alone, or two or more types may be used in combination.

In particular, when titanium oxide (TiO ₂ ) particles, aluminum oxide (Al ₂ O ₃ ) particles, or zirconium oxide (ZrO ₂ ) particles are used as the metal oxide particles (a), interference unevenness in the resin film can be suppressed while It is preferable because it can impart scratch resistance.

When the metal oxide particles (a) used in the resin film of the present invention have a particle size of 10 to 100 nm, a more dense nano-rough structure is formed on the surface of the resin film, and as a result of dispersing frictional force, the metal oxide particles (a) have a resistant It is preferable because it has excellent scratch resistance. Note that the particle size of metal oxide particles (a) in the present invention refers to a particle size determined by a scanning electron microscope (SEM) according to the following method.

(How to determine the particle size of metal oxide particles (a))
A small piece is cut perpendicularly to the surface of the resin film using a microtome, and its cross section is observed and photographed using a scanning transmission electron microscope (SEM) at a magnification of 100,000 times. From the cross-sectional photograph, the particle size distribution of particles present in the film is determined using image analysis software Image-Pro Plus (Nippon Roper Co., Ltd.). Cross-sectional photographs are selected from different arbitrary measurement fields, and the diameters (circular equivalent diameters) of 200 or more particles arbitrarily selected from the cross-sectional photographs are measured, and the horizontal axis is the particle diameter and the vertical axis is plotted as the particle abundance ratio. Obtain the volume-based particle size distribution. In the above-mentioned volume-based particle size distribution, the particle diameter on the horizontal axis is divided into classes at intervals of 10 nm with 0 nm as the starting point, and the abundance ratio of particles on the vertical axis is calculated using the formula ``abundance ratio = applicable particle size.'' Total volume of detected particles/total volume of all detected particles. From the chart of the abundance ratio of particles obtained above, the particle diameter at the top of the peak showing the maximum is read.

The metal oxide particles (a) used in the resin film of the present invention are further a composition (AD) having an acrylic resin (D) on a part or all of the surface of the metal oxide particles (a). It is preferable. By using the composition (AD) containing the acrylic resin (D), the metal oxide particles (a) in the resin film can be nano-dispersed, and when force is applied to the resin film, the force is transferred to the particles. Can be dispersed. As a result, it becomes possible to improve the scratch resistance of the resin film. Further, it is preferable because the transparency of the resin film can also be maintained.

In order to obtain a composition (AD) having an acrylic resin (D) on part or all of the surface of the metal oxide particles (a), the metal oxide particles (a) described below are coated with an acrylic resin (D). Examples include methods of surface treatment. Specifically, the following methods (i) to (iv) are exemplified. In the present invention, surface treatment refers to a treatment in which the acrylic resin (D) is adsorbed and adhered to all or part of the surface of the metal oxide (a) containing a specific element.

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

(ii) A method of sequentially adding and dispersing metal oxide particles (a) and acrylic resin (D) in a solvent.

(iii) A method in which metal oxide particles (a) and acrylic resin (D) are previously dispersed in a solvent, and the resulting dispersion is mixed.

(iv) A method in which the metal oxide particles (a) are dispersed in a solvent and then the acrylic resin (d-2) is added to the resulting dispersion.

Any of these methods can achieve the desired effect.

Further, as an apparatus for dispersing, a dissolver, a high speed mixer, a homomixer, a kneader, a ball mill, a roll mill, a sand mill, a paint shaker, an SC mill, an annular type mill, a pin type mill, etc. can be used.

Further, as a dispersion method, using the above-mentioned apparatus, the rotating shaft is rotated at a circumferential speed of 5 to 15 m/s. The rotation time is 5 to 10 hours.

Moreover, it is more preferable to use dispersion beads such as glass beads during dispersion in terms of improving dispersibility. The diameter of the beads is preferably 0.05 to 0.5 mm, more preferably 0.08 to 0.5 mm, particularly preferably 0.08 to 0.2 mm.

Mixing and stirring can be carried out by shaking the container by hand, using a magnetic stirrer or stirring blade, ultrasonic irradiation, vibration dispersion, and the like.

The presence or absence of adsorption and adhesion of the acrylic resin (D) 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 centrifuged using a Hitachi tabletop ultracentrifuge (CS150NX, manufactured by Hitachi Koki Co., Ltd.) (rotation speed 3,0000 rpm, separation time 30 minutes), and metal oxide particles (a) (and metal oxide After the acrylic resin (D) adsorbed on the surface of the particles (a) is precipitated, the supernatant liquid is removed and the precipitate is concentrated to dryness. The concentrated and dried sediment is analyzed by X-ray photoelectron spectroscopy (XPS) to confirm the presence or absence of the acrylic resin (D) on the surface of the metal oxide particles (a). If it is confirmed that the acrylic resin (D) is present on the surface of the metal oxide particles (a) at 1% by weight or more based on the total 100% by weight of the metal oxide particles (a), the metal oxide particles It is assumed that acrylic resin (D) is adsorbed and attached to the surface of (a).

[Acrylic resin (D)]
As mentioned above, in the resin film of the present invention, the metal oxide particles (a) contained in the insulating phase (A) are composed of a composition (AD) having an acrylic resin (D) on a part or all of its surface. It is preferable that there be. By using the composition (AD) containing the acrylic resin (D), it is possible to nano-disperse the metal oxide particles (a) in the resin film, maintain the transparency of the resin film, and add force to the resin film. When force is applied, the force can be dispersed to the particles. As a result, it becomes possible to improve the scratch resistance of the resin film.

The acrylic resin (D) in the present invention includes a monomer unit (d 1 ) represented by formula (1), a monomer unit (d ₂ ) represented by formula (2), and a monomer unit (d ₂ ) represented by formula (3). It is preferable that the resin has a monomer unit (d ₃ ).

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

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

(In formula (3), the R ₃ group represents a hydrogen element or a methyl group. Also, the R ₅ group represents a hydroxyl group, a carboxyl group, a tertiary amino group, a quaternary ammonium base, a sulfonic acid group, or a phosphoric acid group. (Represents a group.)
Here, the acrylic resin (D) in 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 where n is less than 9 is used, the dispersibility of the metal oxide particles (a) in an aqueous solvent (details of the aqueous solvent will be described later) will be unstable. becomes. When an acrylic resin having a monomer unit in which n in formula (1) is less than 9 is used, the metal oxide particles (a) will violently aggregate in the coating composition, and in some cases, the metal oxide particles (a) may aggregate in the aqueous solvent. ) may settle. As a result, the transparency of the resin film may be impaired, or protrusions may form, leading to defects. On the other hand, acrylic resins having monomer units in which n in formula (1) exceeds 34 have extremely low solubility in aqueous solvents, and therefore agglomeration of the acrylic resins tends to occur in aqueous solvents. Since such aggregates are larger than the wavelength of visible light, it may become impossible to obtain a resin film with good transparency, or interference spots may occur when a coating film is further laminated on the surface layer of the laminated film of the present invention. There are cases. By using a resin having the monomer unit (d ₁ ) represented by the formula (1) as described above, the metal oxide particles (a) are dispersed in an aqueous solvent by moderate interaction, while being dispersed after drying. is a conductive material because multiple metal oxide particles (a) have anisotropy and aggregate finely on the nano-order level in the resin film, forming non-circular insulating domains on the surface of the resin film. The antistatic property can be improved in its resistance to changes over time.

In order for the acrylic resin (D) in the present invention to have a monomer unit (d 1 ) represented by formula (1), the (meth)acrylate monomer (d ₁ ') represented by the following formula ( ₄ ) is required. It is necessary to use and polymerize as a raw material.

The (meth)acrylate monomer ( _d1 ') is preferably a (meth)acrylate monomer in which n in formula (4) is an integer of 9 or more and 34 or less, more preferably a (meth)acrylate monomer of 11 or more and 32 or less. Acrylate monomers, more preferably 13 to 30 (meth)acrylate monomers.

The (meth)acrylate monomer ( _d1 ') is not particularly limited as long as n in formula (4) is 9 or more and 34 or less, but specifically, decyl (meth)acrylate, dodecyl ( meth)acrylate, tridecyl(meth)acrylate, tetradecyl(meth)acrylate, 1-methyltridecyl(meth)acrylate, hexadecyl(meth)acrylate, octadecyl(meth)acrylate, eicosyl(meth)acrylate, docosyl(meth)acrylate, Examples include tetracosyl (meth)acrylate, triacontyl (meth)acrylate, and the like, with dodecyl (meth)acrylate and tridecyl (meth)acrylate being particularly preferred. These may be used alone or in a mixture of two or more.

Moreover, it is important that the acrylic resin (D) in the present invention is a resin having a 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 carbon ring is used, the function as a steric hindrance will be insufficient, causing metal oxide particles (a) to aggregate or In some cases, metal oxide particles (a) may settle in an aqueous solvent. As a result, the transparency of the resin film may be impaired or protrusions may form, leading to defects.

Since such aggregates are larger than the wavelength of visible light, it may become impossible to obtain a resin film with good transparency. In order for the acrylic resin (D) in the present invention to have a monomer unit (d 2 ) represented by formula (2), a (meth)acrylate monomer (d ₂ ') represented by the following formula ( ₅ ) is required. It is necessary to use and polymerize as a raw material.

The (meth)acrylate monomer (d ₂ ') represented by formula (5) is a bridged fused cyclic type (having a structure in which two or more rings each share two elements and are bonded). Examples include compounds having various cyclic structures such as , spirocyclic (having a structure in which two cyclic structures share one carbon element), specifically, bicyclo, tricyclo, and tetracyclo groups. Among these, (meth)acrylate containing a bicyclo group is particularly preferred from the viewpoint of compatibility with the binder.

Examples of the (meth)acrylate containing a bicyclo group include isobornyl (meth)acrylate, bornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, adamantyl (meth)acrylate, and dimethyladamantyl. Examples include (meth)acrylate, and isobonyl (meth)acrylate is particularly preferred.

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

When using an acrylic resin in which the R ₅ group in formula (3) has a monomer unit that does not have any of a hydroxyl group, a carboxyl group, a tertiary amino group, a quaternary ammonium group, a sulfonic acid group, and a phosphoric acid group, the acrylic resin The compatibility of the metal oxide particles (a) in the aqueous solvent becomes insufficient, and the acrylic resin may precipitate in the coating composition, and the metal oxide particles (a) may coagulate or precipitate accordingly, and the metal oxide particles (a) may become unstable during the drying process. a) may aggregate.

Since such aggregates are larger than the wavelength of visible light, it may become impossible to obtain a resin film with good transparency. In order for the acrylic resin (D) in the present invention to have the monomer unit (d 3 ) represented by formula (3), the (meth)acrylate monomer (d ₃ ') represented by formula ( ₆ ) is used as a raw material. It is necessary to use it as a compound and polymerize it.

The following compounds are exemplified as the (meth)acrylate monomer (d ₃ ') represented by formula (6).

Examples of (meth)acrylate monomers having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2,3-dihydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and polyethylene Examples include monoesterified products of polyhydric alcohols such as glycol mono(meth)acrylate and (meth)acrylic acid, or compounds obtained by ring-opening polymerization of ε-caprolactone to the monoesterified products, and in particular, 2-hydroxyethyl ( Preferred are meth)acrylate and 2-hydroxypropyl(meth)acrylate.

Examples of (meth)acrylate monomers having a carboxyl group include α,β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, fumaric acid, and maleic acid, or hydroxyalkyl (meth)acrylates and acid anhydrides. Among them, acrylic acid and methacrylic acid are particularly preferred.

Examples of tertiary amino group-containing monomers include N,N- such as N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, and N,N-dimethylaminopropyl (meth)acrylate. N,N-dialkylamino such as dialkylaminoalkyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylamide, N,N-diethylaminoethyl (meth)acrylamide, N,N-dimethylaminopropyl (meth)acrylamide, etc. Examples include alkyl (meth)acrylamides, and N,N-dimethylaminoethyl (meth)acrylate is particularly preferred.

As the quaternary ammonium base-containing monomer, it is preferable to use a quaternizing agent such as epihalohydrin, benzyl halide, or alkyl halide on the above-mentioned tertiary amino group-containing monomer. Specifically, 2-(methacryloyloxy) ) Ethyltrimethylammonium chloride, 2-(methacryloyloxy)ethyltrimethylammonium bromide, 2-(methacryloyloxy)ethyltrimethylammonium dimethyl phosphate, and other (meth)acryloyloxyalkyl trialkylammonium salts, methacryloylaminopropyltrimethylammonium chloride, methacryloylamino (meth)acryloylaminoalkyl trialkylammonium salts such as propyltrimethylammonium bromide, tetraalkyl (meth)acrylates such as tetrabutylammonium (meth)acrylate, trialkylbenzylammonium (meth)acrylates such as trimethylbenzylammonium (meth)acrylate Among them, 2-(methacryloyloxy)ethyltrimethylammonium chloride is particularly preferred.

Sulfonic acid group-containing monomers include (meth)acrylamide-alkanesulfonic acids such as butylacrylamide sulfonic acid and 2-acrylamido-2-methylpropanesulfonic acid, or sulfoalkyl (meth)acrylates such as 2-sulfoethyl (meth)acrylate. Examples include acrylate, and 2-sulfoethyl (meth)acrylate is particularly preferred.

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

Among these, the acrylic resin (D) in particular is a resin having a monomer unit (d ₃ ) represented by the above formula (3), and the R ₅ group in formula (3) is a hydroxyl group or a carboxyl group. , is preferable because it has a high adsorption power with the metal oxide particles (a) described later and can form a stronger film.

In the present invention, the content of the acrylic resin (D) in the resin film is preferably 5 to 30% by weight, and by setting it within this range, the adsorption of the metal oxide particles (a) and the acrylic resin (D) becomes stronger, and the scratch resistance of the resin film can be improved.

In particular, the content of the acrylic resin (D) is more preferably 5% by weight or more and 30% by weight or less based on the entire resin film, and the content of the acrylic resin (D) in the resin film is 10% by weight. The content is more preferably 30% by weight or less. In the present invention, the content in the resin film refers to the content in the solid content ([(weight of coating composition)−(weight of solvent)]) of the coating composition forming the resin film.

In the resin film of the present invention, when the content of metal oxide particles (a) in the resin film is 15 to 50% by weight based on the entire resin film, the metal oxide particles (a) are filled in the resin film. By doing so, the conductive material is prevented from being exposed on the surface of the resin film, and the antistatic performance is easily stabilized. Further, by increasing the area of the particle component, the hardness of the entire resin film is improved and scratch resistance is excellent, which is preferable. The content of metal oxide particles (a) is preferably 20 to 50% by weight, more preferably 30 to 50% by weight.

[Binder resin]
The resin film and layer (X) of the present invention preferably contain a binder resin as a component. Binder resins include known acrylic resins, polyester resins, urethane resins, and copolymers thereof.

As the urethane resin, for example, a resin having a structural unit derived from polyisocyanate compound (I) and a polyol (II) unit can be used. Note that the polyurethane resin may have other units (for example, carboxylic acid units, amine units, etc.) other than the polyisocyanate compound (I) units and polyol (II) units.

Examples of the polyurethane resin include polyacrylic polyurethane resin, polyether polyurethane resin, and polyester polyurethane resin. The polyurethane resins may be used alone or in combination of two or more.

The polyisocyanate compound (I) is not particularly limited as long as it has two or more isocyanate groups.

Examples of the polyisocyanate compound (I) include polyisocyanates (e.g., aliphatic polyisocyanates, alicyclic polyisocyanates, araliphatic polyisocyanates, aromatic polyisocyanates, etc.), modified polyisocyanates [or derivatives, e.g. , multimers (dimers, trimers, etc.), carbodiimides, biurets, allophanates, uretdiones, modified polyamines, etc.]. The polyisocyanate compound (I) may be used alone or in combination of two or more. The aliphatic polyisocyanate is not particularly limited, but includes, for example, aliphatic diisocyanates [e.g., alkanediisocyanates (e.g., tetramethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, dodecamethylene diisocyanate, lysine diisocyanate). , 2-methylpentane-1,5-diisocyanate, 3-methylpentane-1,5-diisocyanate and other C2-20 alkaned diisocyanates, preferably C4-12 alkaned diisocyanates, etc.)], aliphatic having 3 or more isocyanate groups Examples include polyisocyanates (eg, aliphatic tri- to hexaisocyanates such as 1,4,8-triisocyanatooctane), and the like.

The alicyclic polyisocyanate is not particularly limited, but includes, for example, alicyclic diisocyanate {for example, cycloalkane diisocyanate (for example, C5-8 cycloalkane diisocyanate such as methyl-2,4- or 2,6-cyclohexane diisocyanate) ), isocyanatoalkylcycloalkane isocyanates [e.g., isocyanato C1-6 alkyl C5-10 cycloalkane isocyanates such as 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI)], di( isocyanatoalkyl)cycloalkane [e.g., di(isocyanatoC1-6alkyl)C5-10 cycloalkane such as hydrogenated xylylene diisocyanate], di(isocyanatocycloalkyl)alkane [e.g., hydrogenated diphenylmethane-4,4' - bis(isocyanato C5-10 cycloalkyl) C1-10 alkanes such as diisocyanate (4,4'-methylenebiscyclohexyl isocyanate), etc.), polycycloalkane diisocyanate (norbornane diisocyanate, etc.)}, having 3 or more isocyanate groups Examples include alicyclic polyisocyanates (for example, alicyclic tri- to hexaisocyanates such as 1,3,5-triisocyanatocyclohexane).

Examples of the araliphatic polyisocyanate include, but are not particularly limited to, araliphatic diisocyanates {for example, di(isocyanatoalkyl)arene [for example, xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI) (1, bis(isocyanatoC1-6 alkyl)C6-12 arenes such as 3- or 1,4-bis(1-isocyanato-1-methylethyl)benzene), aromatic aliphatic polyisocyanates having 3 or more isocyanate groups (For example, aromatic aliphatic tri- to hexaisocyanates, etc.).

Aromatic polyisocyanates include, but are not particularly limited to, aromatic diisocyanates {for example, arene diisocyanates [for example, o-, m- or p-phenylene diisocyanate, chlorophenylene diisocyanate, tolylene diisocyanate, naphthalene diisocyanate (NDI), etc. C6-12 arene diisocyanates, etc.], di(isocyanatoaryl)alkanes [e.g., diphenylmethane diisocyanate (MDI) (2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, etc.), bis(isocyanates such as toridine diisocyanate), C6-10 aryl) C1-10 alkane, etc.], aromatic polyisocyanates having three or more isocyanate groups (for example, aromatic polyisocyanates such as 4,4'-diphenylmethane-2,2',5,5'-tetraisocyanate) (tri- to hexaisocyanate, etc.).

In the present invention, it is preferable to use an alicyclic polyisocyanate as the polyisocyanate compound (I) from the viewpoint of crack resistance.

Polyol (II) is not particularly limited as long as it has two or more hydroxyl groups.

Examples of the polyol (II) include polyacrylic polyols, polyester polyols, polyether polyols, and polyurethane polyols. Polyol (II) may be used alone or in combination of two or more.

Examples of polyacrylic polyols include copolymers having (meth)acrylic acid ester units and units derived from components having hydroxyl groups (component units having hydroxyl groups). The polyacrylic polyol may have units other than component units having (meth)acrylic acid ester units and hydroxyl groups.

Examples of the polyester polyol include a copolymer having a polyhydric carboxylic acid component unit and a polyol component unit. The polyester polyol may have units other than the polyhydric carboxylic acid component unit and the polyol component unit.
Examples of polyether polyols include copolymers obtained by adding alkylene oxide to polyhydric alcohols. The polyhydric alcohol is not particularly limited, and for example, the dihydric alcohols mentioned above can be used. Polyhydric alcohols may be used alone or in combination of two or more.

Further, 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. Alkylene oxides may be used alone or in combination of two or more. The polyurethane resin may contain a chain extender as a constituent (or may have a constituent unit derived from a chain extender).

Chain extenders are not particularly limited, and include, for example, glycols (e.g., C2-6 alkanediols such as ethylene glycol, 1,4-butanediol, neopentyl glycol, and 1,6-hexanediol), polyhydric alcohols, etc. Common chain extenders such as C2-6 alkanetri-hexaols such as glycerin, trimethylolpropane, pentaerythritol, etc., diamines (eg, ethylenediamine, hexamethylenediamine, etc.) may be used.

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

Furthermore, it is preferable that the resin film of the present invention contains a urethane component together with an ether component. When the resin film or layer (X) contains the urethane component and the ether component, the compatibility is controlled, and when the resin film or layer (X) contains the metal oxide particles (a), the resin film or layer (X) It becomes easy to form the insulating phase (A) on the surface. The method for containing the urethane component and the ether component in the resin film or layer (X) is not particularly limited, but includes a method using a urethane resin component having an ether bond. Specifically, a urethane resin obtained by reacting a polyether polyol compound and an isocyanate compound is preferable. In the present invention, having an ether component means having an ether bond, and having a urethane component means having a urethane bond.

When the urethane resin component as described above is used, the hydrophilicity of the urethane resin component becomes high. Therefore, a composition (AD) having an acrylic resin (D) on part or all of the surface of the metal oxide particles (a) or the metal oxide particles (a), and a coating composition (x) containing a urethane resin component. When the layer (X) is formed by applying the urethane resin component to at least one side of the polyester film that is the supporting base material and then heating it to form the layer (X), the highly hydrophilic urethane resin component is applied to the side of the polyester film that is the base layer in the layer (X). A composition (AD) having an acrylic resin (D) on a part or all of the metal oxide particles (a) and the surface of the metal oxide particles (a) which are unevenly distributed and have relatively low hydrophilicity is a layer (X). A phase-separated structure can be formed in which the phase separation structure is unevenly distributed near the surface. By having a phase separation structure that unevenly distributes the metal oxide particles (a) near the surface of the layer (X) and the urethane resin component near the interface with the base material layer of the layer (X), the surface of the layer (X) Because domains (island components) with high elastic modulus can be formed in the vicinity, scratch resistance is exhibited, while the inner layer of layer (X) exhibits workability due to stress relaxation by the flexible urethane resin component. , is preferable because it can achieve both high levels of scratch resistance and workability.

[Conductive compound (b)]
The resin film of the present invention preferably contains a conductive compound (b) as a component of the conductive phase (B). The conductive compound (b) is not particularly limited, and includes, for example, carbon-based materials such as carbon nano-tubes (CNTs), polymeric materials having a conductive structure typified by polythiophene structure, and free acid state. Acidic polymers and the like can be used alone or in combination. From the viewpoint of the initial characteristics of antistatic performance, it is particularly preferable to use a mixed component of a compound having a polythiophene structure and an acidic polymer in a free acid state.

As the compound having a polythiophene structure, for example, a compound having a structure in which the 3- and 4-positions of the thiophene ring are substituted can be used. Furthermore, compounds in which oxygen atoms are bonded to the carbon atoms at the 3rd and 4th positions of the thiophene ring can be suitably used. If a hydrogen atom or a carbon atom is directly bonded to the carbon atom, it may not be easy to make the coating liquid water-based. The above compound can be produced, for example, by the methods disclosed in JP-A-2000-6324, European Patent No. 602713, and US Pat. No. 5,391,472, but methods other than these may also be used.

For example, after obtaining 3,4-ethylenedioxythiophene using an alkali metal salt of 3,4-dihydroxythiophene-2,5,-dicarboxyester as a starting material, potassium peroxodisulfate and sulfuric acid are added to an aqueous polystyrene sulfonic acid solution. By introducing iron and the previously obtained 3,4-ethylenedioxythiophene and allowing them to react, acidic polymers such as polystyrene sulfonic acid are formed into polythiophenes such as poly(3,4-ethylenedioxythiophene). Complexed compositions can be obtained.

In addition, as an aqueous coating composition containing poly-3,4-ethylenedioxythiophene and polystyrene sulfonic acid, H. C. A product sold as "Baytron" P by Starck (Germany) can be used.

On the other hand, examples of acidic polymers in a free acid state include polymeric carboxylic acids, polymeric sulfonic acids, and polyvinylsulfonic acids. Examples of the polymeric carboxylic acid include polyacrylic acid, polymethacrylic acid, and polymaleic acid. Examples of the polymeric sulfonic acid include polystyrene sulfonic acid, and polystyrene sulfonic acid is particularly preferred from the viewpoint of antistatic properties. Note that the free acid may be in the form of a partially neutralized salt. Further, it can also be used in a form copolymerized with other copolymerizable monomers, such as acrylic esters, methacrylic esters, and styrene. The molecular weight of the polymeric carboxylic acid or polymeric sulfonic acid is not particularly limited, but in terms of stability and antistatic properties of the coating material, the weight average molecular weight is preferably 1000 or more and 1000000 or less, more preferably 5000 or more. 150,000 or less. Part of the composition may contain alkali salts such as lithium salts and sodium salts, ammonium salts, etc., within a range that does not impede the characteristics of the invention. Salts with neutralized polyanions are also considered to act as dopants. This is because polystyrene sulfonic acid and ammonium salt, which function as very strong acids, shift their equilibrium to the acidic side due to the progress of the equilibrium reaction after neutralization.

[Other ingredients]
In the resin film of the present invention, when the conductive phase (B) is formed from a coating composition containing at least one compound selected from a melamine compound, an oxazoline compound, a carbodiimide compound, an isocyanate compound, and an epoxy compound, the resin Since the film has a dense crosslinked structure, it is preferred because it has excellent scratch resistance and stability in antistatic performance. Therefore, the conductive phase (B) of the resin film of the present invention preferably contains a component derived from a melamine compound, an oxazoline compound, a carbodiimide compound, an isocyanate compound, and an epoxy compound.
In particular, when a coating composition (x) containing a melamine compound, an oxazoline compound, or a carbodiimide compound is used, nitrogen-containing functional groups are introduced into the resin film, which improves polarity and improves the coating layer and Adhesion to metal layers such as sputtered layers and vapor deposited layers is improved, which is preferable.
Furthermore, from the viewpoint of compatibility with conductivity, as some melamine compounds may show an increase in resistance value when coexisting with conductive materials, at least one compound selected from oxazoline compounds, carbodiimide compounds, and isocyanate compounds should be used. Preferably, a coating composition (x) containing seeds is used.

On the other hand, if it is necessary to achieve both optical properties such as transparency, it is possible to use two or more types of crosslinking agents such as melamine compounds, oxazoline compounds, carbodiimide compounds, isocyanate compounds, and epoxy compounds. preferable. By using two or more types of crosslinking agents together, we maintain the crosslinking properties necessary to improve conductivity stability and scratch resistance, while reducing the amount of each individual material added to improve compatibility with the resin component. It becomes easy to attach. Among these, it is preferable to use a coating composition (x) containing at least two selected from oxazoline compounds, carbodiimide compounds, and isocyanate compounds.

Examples of melamine compounds include melamine, methylolated melamine derivatives obtained by condensing melamine and formaldehyde, compounds obtained by reacting methylolated melamine with a lower alcohol to partially or completely etherify it, and mixtures thereof. Can be used. Specifically, compounds having a triazine and a methylol group are particularly preferred. The melamine compound in the present invention refers to a component derived from a melamine compound when the melamine compound described below forms a crosslinked structure with a urethane resin, an acrylic resin, an oxazoline compound, a carbodiimide compound, an isocyanate compound, an epoxy compound, etc. means. Further, the melamine compound may be a monomer, a condensate consisting of a dimer or more, or a mixture thereof. As the lower alcohol used for etherification, methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butanol, isobutanol, etc. can be used. The group includes an imino group, a methylol group, or an alkoxymethyl group such as a methoxymethyl group or a butoxymethyl group in one molecule.Imino group type methylated melamine resin, methylol group type melamine resin, methylol group type methylated melamine resin, completely alkyl type methylated melamine resin, etc. Among them, methylolated melamine resin is most preferred. Further, in order to promote thermal curing of the melamine compound, an acidic catalyst such as p-toluenesulfonic acid may be used.

When such melamine compounds are used, not only does the self-condensation of the melamine compound increase the hardness of the coating and improve scratch resistance, but also the reaction between the hydroxyl groups and carboxyl groups contained in the acrylic resin and the melamine compound progresses. , a stronger resin film can be obtained, and a film with excellent scratch resistance can be obtained.

The oxazoline compound is the oxazoline compound described below, or when the oxazoline compound forms a crosslinked structure with urethane resin (d-2), acrylic resin (D), melamine compound, isocyanate compound, or carbodiimide compound, oxazoline compound is It means a component derived from a compound. The oxazoline compound is not particularly limited as long as it has an oxazoline group as a functional group, but it contains at least one monomer containing an oxazoline group and at least one other monomer. It is preferable to use an oxazoline group-containing copolymer obtained by copolymerizing monomers.

Monomers containing an oxazoline group include 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-oxazoline, etc. can be used, and one type or a mixture of two or more of these can also be used. Among them, 2-isopropenyl-2-oxazoline is suitable because it is industrially easily available.

In the oxazoline compound, at least one other monomer used for the monomer containing an oxazoline group is not particularly limited as long as it is a monomer copolymerizable with the monomer containing the oxazoline group, but for example, acrylic Acrylic acid esters or methacrylic esters such as methyl acid, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, acrylic acid, Unsaturated carboxylic acids such as methacrylic acid, itaconic acid, and maleic acid; unsaturated nitriles such as acrylonitrile and methacrylonitrile; unsaturated amides such as acrylamide, methacrylamide, N-methylolacrylamide, and N-methylolmethacrylamide; acetic acid. Vinyl, vinyl esters such as vinyl propionate, vinyl ethers such as methyl vinyl ether and ethyl vinyl ether, olefins such as ethylene and propylene, and halogen-containing α,β-unsaturated monomers such as vinyl chloride, vinylidene chloride, and vinyl fluoride. α,β-unsaturated aromatic monomers such as styrene, α-methylstyrene, etc. can be used, and one type or a mixture of two or more of these can also be used.

The carbodiimide compound in the present invention refers to the carbodiimide compound described below, or when the carbodiimide compound forms a crosslinked structure with a urethane resin, acrylic resin, melamine compound, isocyanate compound, or oxazoline compound, a component derived from the carbodiimide compound. means. The carbodiimide compound is not particularly limited as long as the compound has one or more carbodiimide groups or cyanamide groups having a tautomeric relationship as a functional group in the molecule.

Known techniques can be applied to the production of carbodiimide compounds, and generally, carbodiimide compounds are obtained by polycondensing diisocyanate compounds in the presence of a catalyst. As the diisocyanate compound that is the starting material for the carbodiimide compound, aromatic, aliphatic, alicyclic diisocyanates, etc. can be used, and specifically, tolylene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, and cyclohexane diisocyanate. , isophorone diisocyanate, dicyclohexyl diisocyanate, etc. can be used.

[Method of measuring characteristics and evaluating effectiveness]
The method of measuring the characteristics and the method of evaluating the effect in the present invention are as follows. Note that Example 6 below is a reference example.

(1) Measurement of surface α (1-1) Conductivity of surface α using AFM The conductivity of the layer surface was measured using AFM (Dimension Icon manufactured by Burker Corporation) and analyzed using conductive measurement mode (conductive AFM). carried out. Specifically, measurements were carried out under the following conditions according to the conductive AFM manual. The sample was fixed using the following method to ensure conductivity from the layer surface to the sample stage. First, a resin film was cut into a size of 1 cm x 1 cm. Subsequently, the resin film was placed on a stainless steel sample stand so that the surface of the layer whose conductivity was to be measured faced upward. Furthermore, the resin film was fixed to the sample stage using conductive tape (manufactured by Nissin EM Co., Ltd., carbon double-sided tape for SEM (aluminum base, 8 mm width)) to cover the four sides of the resin film approximately 3 mm from the end.
Measuring device: Atomic force microscope (AFM) manufactured by Barker Corporation
Measurement mode: Conductive AFM (contact mode)
Cantilever: Bruker AXS SCM-PIC
(Material: Si, Spring constant K: 0.2 (N/m), Tip radius of curvature R: 20 (nm))
Measurement atmosphere: 23℃/in the air Measurement range: 1 (μm) Square resolution: 512 x 512
Cantilever movement speed: 10 (μm/s)
Maximum pushing load: 10 (nN).
Applied voltage: 10V
After measurement, select the "C-AFM Current" image and binarize the image displayed on the screen with "ScionImage" (maximum value: 10 nA, minimum value: 0 pA, threshold value 180 (black = 0, white = 255). , in a gray scale representing black to white in 256 steps, a conductivity image was created by setting the area where 10 nA or more flows to 255 (white) and the area where 0 pA is 0 (black), and the obtained conductivity In the image, areas with high current values expressed in shades of gray scale 180 or higher are colored white, areas with low current values expressed in shades below gray scale 180 are colored black), and the conductivity of the surface α is It was made into a statue. Note that the operation of performing the binarization process according to the above procedure corresponds to dividing the image into an insulating region and a conductive region using a current value of 7.2 nA as a boundary value.

(1-2) The conductive image of 1 μm x 1 μm obtained from the presence/absence of insulating phase (A) and conductive phase (B) (1-1) is divided vertically and horizontally into 40 sections, and divided into 1600 regions of 25 nm x 25 nm. . Among the 1,600 regions, if one region has either solid black or solid white, it is considered to have an insulating phase (A) and a conductive phase (B). That is, when there is no bias in conductivity and an image consisting only of the insulating phase (A) or an image consisting only of the conductive layer (B) is obtained, or when the size of any phase is less than 25 nm square. It was determined that the structure does not have two phases: an insulating phase (A) and a conductive phase (B).
Furthermore, the measurement range was arbitrarily selected and the measurement was carried out 10 times, and if a black part and a white part were observed 8 times or more, it was determined that the sample had an insulating phase (A) and a conductive phase (B).

(1-3) Conductivity of conductive phase (B) and insulating phase (A) In the 1600 regions in the conductive image determined in (1-1), all the regions are solid black in the binarized image. Conductivity data was extracted for all regions, and the average value was taken as the conductivity (I _A ) of the insulating phase (A). Similarly, in the 1,600 regions in the conductive image obtained in (1-1), the elastic modulus of all the regions in which one region is solid white is measured, and the average value is calculated as the conductivity of the conductive phase (B). ( _IB ). Further, the measurement range was arbitrarily selected and the measurement was performed 10 times, and the average value of the total of 8 times excluding the maximum value and minimum value was adopted.

(1-4) Regarding the conductive image obtained using the area ratio (1-1) of the insulating phase (A), calculate the area ratio of the black part using software (image processing software ImageJ/Developer: National Institutes of Health (NIH)) ) was calculated as the sum of the occupied area ratios using the Analyze Particles function, and was taken as the area ratio of the insulating phase (A).

(1-5) Regarding the conductivity image obtained using the average domain diameter (1-1) of the insulating phase (A), the average domain diameter of the black part was calculated using software (image processing software ImageJ/Developer: National Institutes of Health) NIH)) Analyze
The radius value calculated using circular approximation using the Particles (particle analysis) function was employed as the average domain diameter. Regarding the handling of data at the edges of the measurement area, Exclude on edges in Analyze Particles was enabled to exclude them from the measurement.

(1-6) Containment of metal oxide (a) in insulating phase (A) By observing the surface α at a magnification of 100,000 times using a SEM (scanning electron microscope), the surface of the polyester film The insulating phase (A) of α was subjected to elemental analysis by EDX (energy dispersive X-ray spectroscopy) to determine whether the metal oxide (a) was contained.

Specifically, regarding the insulating phase (A) on the surface α observed with a field emission scanning electron microscope (model number S-4800) manufactured by Hitachi High-Technologies, QUANTAX manufactured by BrukerAXS
When element detection is measured using the Flat QUAD System (model number Xflash 5060FQ) and at least one metal element selected from the group consisting of Si, Al, Ti, Zr, Se, and Fe is detected, metal oxide (a ).
In addition, when 50% or more of the insulating phase (A) on the surface α contains the metal oxide (a), the insulating phase (A) on the surface α contains the metal oxide (a). Then I decided.

(1-7) Elastic modulus of surface α by AFM The surface elastic modulus of the layer surface was measured using AFM (Dimension Icon manufactured by Burker Corporation) in PeakForceQNM mode, and the attached analysis was performed from the obtained force curve. Software “NanoScope Analysis
Analysis based on the JKR contact theory was performed using "V1.40" to determine the surface elastic modulus.

Specifically, first, the warpage sensitivity, spring constant, and tip curvature of the cantilever were configured according to the PeakForceQNM mode manual. Note that the spring constant and tip curvature vary depending on the individual cantilever, but as a range that does not affect the measurement, the spring constant is 0.1 (N/m) or more and 0.4 (N/m) or less, and the tip curvature radius is 25 ( nm) A cantilever satisfying the following conditions was adopted and used for measurement. The measurement conditions are shown below.
Measuring device: Atomic force microscope (AFM) manufactured by Barker Corporation
Measurement mode: Force curve was collected in Ramp mode Cantilever: Bruker AXS SCM-PIC
(Material: Si, Spring constant K: 0.2 (N/m), Tip radius of curvature R: 20 (nm))
Measurement atmosphere: 23°C, air Number of measurements: 10 points Cantilever movement speed: 10 (μm/s)
Maximum pushing load: 10 (nN).

Ramp mode was used for the measurement. First, the location for measurement was determined from the conductive phase (B) and insulating phase (A) obtained by the conductivity measurement described above in Scan mode, and the location was moved to the center of the image using OFFSET. Next, the mode was switched to Ramp mode, and a force curve was collected.

Next, the obtained force curve was analyzed using analysis software "NanoScope Analysis V1.40" to obtain the surface elastic modulus. Similar measurements were repeated 10 times for each of the conductive phase (B) and the insulating phase (A), and the average value of a total of 8 measurements excluding the maximum and minimum values was adopted as the elastic modulus G _A and G _B of each phase. did.

(2) Scratch resistance The presence or absence of scratches on the surface of the resin film after performing the scratching treatment under the following conditions was visually confirmed, and the following evaluation was performed.
[Abrasion Treatment] The surface of the resin film is rubbed with steel wool (Bonstar #0000, manufactured by Nippon Steel Wool Co., Ltd.) 10 times at a load of 200 g/cm ² .
S: No scratches A: 1 to 5 scratches B: 6 to 10 scratches C: 11 to 15 scratches D: 16 or more scratches.

(3-1) Haze (transparency)
Haze was measured using a turbidity meter "NDH5000" manufactured by Nippon Denshoku Industries Co., Ltd. after leaving the resin film sample for 40 hours under normal conditions (23°C, relative humidity 50%).
The method was conducted in accordance with K 7136 "How to determine the haze of transparent materials" (2000 edition). Note that the measurement was performed by irradiating light from the side where the surface α of the sample was laminated. Ten square samples each having a side of 50 mm were prepared, and the average value of each measurement was taken once, a total of 10 times, and the haze value of the sample was taken as the haze value of the sample.

(3-2) Haze after abrasion evaluation After abrasion treatment was performed in the same manner as in (2), haze measurement was performed again using the above method.

(4) Interference unevenness A black glossy tape (manufactured by Yamato Co., Ltd., vinyl tape No. 200-50-21: black) was attached to the opposite side of the surface α of the resin film so as not to trap air bubbles.

Place this sample 30 cm directly under a 3-wavelength fluorescent lamp (manufactured by Panasonic Corporation, 3-wavelength daylight white (F・L 15EX-N 15W)) in a dark room, and visually observe the degree of interference unevenness while changing the viewing angle. The following evaluations were made. A score of B or higher was considered good.

A: The interference unevenness is almost invisible. B: The interference unevenness is slightly visible. C: The interference unevenness is strong.

(5) Antistatic performance (5-1) Initial antistatic property Antistatic property was measured by surface resistivity. To measure surface resistivity, the resin film to be measured is left for 24 hours at 23% relative humidity and 25°C, and in this atmosphere, a digital ultra-high resistance/microcurrent meter R8340A and a resistivity chamber 12702A (Advantest Co., Ltd.) are used. (Main electrode: Φ50 mm, counter electrode: Φ103 mm), after applying an applied voltage of 100 V for 10 seconds, measurement was performed. The unit is Ω/□. The surface α of the sample was evaluated, and the average value of a total of 10 measurements was taken as the surface resistivity (R1) of the sample.
A value of 1×10 ⁸ Ω/□ or less was considered good, a value of 1×10 ¹⁰ Ω/□ or less was considered a practically usable level, and a value exceeding 1×10 ¹⁰ Ω/□ was considered a practically problematic level.

(5-2) Antistatic property after 1 month After creating the resin film, it was stored for 30 days at 23% relative humidity and 25°C with the side for antistatic evaluation of the resin film facing up. After that, evaluation was performed in the same manner as in (5-1). From the obtained value, calculate the rate of change over time (initial surface resistivity (Ω/□)/surface resistivity after one month (Ω/□). If the rate of change over time is less than 3 times, it is good; less than 10 times. was set at a practical level.

(5-3) Antistatic properties during drying After the resin film was prepared, it was evaluated in the same manner as in (5-1) except that it was left to stand for 1 hour at 105°C and 5% relative humidity. was carried out. (Dry surface resistivity (Ω/□)/initial surface resistivity (Ω/□)) is preferably 1 or less, and less than 5 times is considered a practical level.

In addition, the characteristics of the resin films obtained in the following examples and comparative examples are shown in the table.

<Reference example>
<Reference Example 1> Emulsion (EM-1) containing a composition (AD) having an acrylic resin (D) on the surface of metal oxide particles (a)
100 parts by weight of isopropyl alcohol as a solvent was charged into an ordinary acrylic resin reaction tank equipped with a stirrer, a thermometer, and a reflux condenser, and the mixture was heated and stirred to maintain the temperature at 100°C.
In this, as (meth)acrylate (d'-1), 40 parts by weight of eicosyl methacrylate with n=19, and as (meth)acrylate (d'-2), 40 parts by weight of isobornyl methacrylate having two rings. A mixture of 20 parts by weight of 2-hydroxyethyl acrylate was added dropwise over a period of 3 hours as a (meth)acrylate (d'-3) having a hydroxyl group. After the dropwise addition was completed, the mixture was heated at 100° C. for 1 hour, and then an additional catalyst mixture containing 1 part by weight of t-butylperoxy 2-ethylhexanoate was charged. Next, the mixture was heated at 100° C. for 3 hours and then cooled to obtain an acrylic resin (D-1).

Using metal oxide particles "NanoTek" Al ₂ O ₃ slurry (manufactured by CI Kasei Co., Ltd., number average particle diameter 60 nm: A-1) containing Al element as metal oxide particles (a), "NanoTek" was added to an aqueous solvent. "Al ₂ O ₃ slurry and the above acrylic resin (D-1) were added in order and dispersed by the following method to form a mixed composition (AD) containing metal oxide particles (a) and acrylic resin (D-1). An emulsion (EM-1) was obtained. (Method (ii) above.)
The addition amount ratio (weight ratio) of the metal oxide particles (a) and the acrylic resin (D-1) was (A)/(D-1) = 50/50 (the weight ratio is calculated to the first decimal place). (calculated by rounding to the nearest whole number). The dispersion treatment was performed using a homomixer and rotated at a circumferential speed of 10 m/s for 5 hours. In addition, the weight ratio of the metal oxide particles (a) and the acrylic resin (B) in the finally obtained composition (BA) was (A)/(D-1) = 50/50 ( Note that the weight ratio was determined by rounding to the first decimal place).

The obtained composition (AD) was centrifuged using a Hitachi tabletop ultracentrifuge (CS150NX, manufactured by Hitachi Koki Co., Ltd.) (rotation speed 3000 rpm, separation time 30 minutes) to obtain metal oxide particles (a). After precipitating the acrylic resin (D) adsorbed on the surface of the metal oxide particles (a), the supernatant liquid was removed and the precipitate was concentrated to dryness. As a result of analyzing the concentrated and dried precipitate by X-ray photoelectron spectroscopy (XPS), it was confirmed that the acrylic resin (D) was present on the surface of the metal oxide particles (a). In other words, the acrylic resin (D) is adsorbed and adhered to the surface of the metal oxide particles (a), and the resulting composition (AD) is applied to the surface of the metal oxide particles (a). ) was found to correspond to particles with

<Reference example 2>
Emulsion (EM-2) containing a composition (AD) having an acrylic resin (D) on the surface of metal oxide particles (a)
The procedure was the same as in Reference Example 1, except that the ratio (weight ratio) of metal oxide particles (a) and acrylic resin (D-1) was changed to (A)/(D-1) = 60/40. EM-2 was obtained.

<Reference example 3>
Emulsion (EM-3) containing a composition (AD) having an acrylic resin (D) on the surface of metal oxide particles (a)
The procedure was the same as in Reference Example 1, except that the ratio (weight ratio) of metal oxide particles (a) and acrylic resin (D-1) was changed to (A)/(D-1) = 70/30. EM-3 was obtained.

<Reference example 4>
Emulsion (EM-4) containing a composition (AD) having an acrylic resin (D) on the surface of metal oxide particles (a)
Reference example except that metal oxide particles containing Al element ("NanoTek" Al ₂ O ₃ slurry (manufactured by CI Kasei Co., Ltd., number average particle diameter 50 nm): A-2) were used as metal oxide particles (a). EM-4 was obtained in the same manner as in Example 2.

<Reference example 5>
Emulsion (EM-5) containing a composition (AD) having an acrylic resin (D) on the surface of metal oxide particles (a)
Reference example except that metal oxide particles containing Al element (“NanoTek” Al ₂ O ₃ slurry (manufactured by CI Kasei Co., Ltd., number average particle diameter 200 nm): A-3) were used as metal oxide particles (a). EM-5 was obtained in the same manner as in Example 2.

<Reference example 6>
Emulsion (EM-6) containing a composition (AD) having an acrylic resin (D) on the surface of metal oxide particles (a)
Same as Reference Example 2 except that tin-antimony-based oxide particles (T-1 series (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd., number average particle diameter 60 nm): A-4) were used as the metal oxide particles (a). EM-6 was obtained in the same manner.

<Reference example 7>
Emulsion (EM-7) containing a composition (AD) having an acrylic resin (D) on the surface of metal oxide particles (a)
The same procedure as in Reference Example 2 was used, except that "Nano Youth (registered trademark)" ZR (manufactured by Nissan Chemical Industries, Ltd., number average particle diameter 90 nm): A-5 containing Zr element was used as the metal oxide particles (a). EM-7 was obtained by the method.

<Reference example 8>
Emulsion (EM-8) containing a composition (AD) having an acrylic resin (D) on the surface of metal oxide particles (a)
Reference Example 2 except that "Snowtex (registered trademark)" colloidal silica slurry containing Si element (manufactured by Nissan Chemical Industries, Ltd., number average particle diameter 80 nm): A-6 was used as the metal oxide particles (a). EM-8 was obtained in the same manner as above.

<Reference example 9>
Emulsion (EM-9) containing a composition (AD) having an acrylic resin (D) on the surface of metal oxide particles (a)
100 parts by weight of isopropyl alcohol as a solvent was charged into an ordinary acrylic resin reaction tank equipped with a stirrer, a thermometer, and a reflux condenser, and the mixture was heated and stirred to maintain the temperature at 100°C.
In this, as (meth)acrylate (d'-1), 40 parts by weight of eicosyl methacrylate with n=19, and as (meth)acrylate (d'-2), 40 parts by weight of isobornyl methacrylate having two rings. 10 parts by weight of 2-hydroxyethyl acrylate and 10 parts by weight of 2,2,2-trifluoroethyl acrylate (d'-4) as (meth)acrylate (d'-3) having other hydroxyl groups. The mixture was added dropwise over 3 hours. After the dropwise addition was completed, the mixture was heated at 100° C. for 1 hour, and then an additional catalyst mixture containing 1 part by weight of t-butylperoxy 2-ethylhexanoate was charged. Next, the mixture was heated at 100° C. for 3 hours and then cooled to obtain an acrylic resin (D-2).

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

<Reference Example 10> Preparation of acrylic resin (D-3) In a nitrogen gas atmosphere and at room temperature (25°C), 100 parts by weight of water and 1 weight of polyethylene glycol monomethacrylate (the repeating unit of ethylene oxide is 16) were placed in a container 1. 1 part and 0.5 part by weight of ammonium persulfate were charged, and the temperature was raised to 70°C to dissolve the solution to obtain a solution 1 at 70°C. Next, at room temperature (25° C.), the following raw materials were added to container 2 in the following ratios and stirred to obtain solution 2.
- 5 mole parts of polyethylene glycol monomethacrylate (16 repeating units of ethylene oxide) - 62 mole parts of methyl methacrylate - 30 mole parts of ethyl acrylate - 2 mole parts of acrylic acid - 1 mole part of N-methylol acrylamide, then 100 parts by weight 50 parts by weight of water was added to Solution 2 to obtain Solution 3. Solution 1 was transferred to a reactor under a nitrogen gas atmosphere, and solution 3 was continuously added dropwise to solution 1 over 3 hours while maintaining the temperature of the solution in the reactor at 70°C. After the addition was completed, the mixture was further stirred at 85 degrees for 2 hours, cooled to 25 degrees, and neutralized with aqueous ammonia to obtain an acrylic resin (D-3) emulsion.

<Reference example 11>
Emulsion (EM-10) containing a composition (AD) having an acrylic resin (D) on the surface of metal oxide particles (a)
The procedure was the same as in Reference Example 1, except that the ratio (weight ratio) of metal oxide particles (a) and acrylic resin (D-1) was changed to (A)/(D-1) = 20/80. EM-10 was obtained.

<Reference example 12>
Emulsion (EM-11) containing a composition (AD) having an acrylic resin (D) on the surface of metal oxide particles (a)
The procedure was the same as in Reference Example 1, except that the ratio (weight ratio) of metal oxide particles (a) and acrylic resin (D-1) was changed to (A)/(D-1) = 80/20. EM-11 was obtained.

<Reference example 13>
Emulsion (EM-12) containing a composition (AD) having an acrylic resin (D) on the surface of metal oxide particles (a)
The same procedure as Reference Example 2 was used, except that "Nano Youth (registered trademark)" ZR (manufactured by Nissan Chemical Industries, Ltd., number average particle diameter 20 nm): A-7 containing Zr element was used as the metal oxide particles (a). EM-12 was obtained in a similar manner.

<Reference Example 14> Conductive compound B-1
In 1887 parts by weight of an aqueous solution containing 20.8 parts by weight of polystyrene sulfonic acid, an acidic polymer compound, 49 parts by weight of a 1% by weight iron(III) sulfate aqueous solution and 8.8 parts by weight of 3,4-ethylenedioxythiophene, a thiophene compound. 8 parts by weight and 117 parts by weight of a 10.9% by weight aqueous peroxodisulfuric acid solution were added. This mixture was stirred at 18°C for 23 hours. Next, 154 parts by weight of a cation exchange resin and 232 parts by weight of an anion exchange resin were added to this mixture, and after stirring for 2 hours, the ion exchange resin was filtered off to obtain poly(3,4-ethylenedioxythiophene). ) and polystyrene sulfonic acid, an aqueous dispersion B-1 (solid content concentration: 1.3% by weight) was obtained.

<Reference Example 15> Conductive compound B-2
Polystyrene sulfonate ammonium salt (weight average molecular weight: 75,000) was diluted with water to obtain polystyrene sulfonate ammonium salt aqueous solution B-2 (solid content concentration 5% by weight).

<Example 1>
First, coating composition 1 was prepared as follows.
<Coating composition>
Coating composition 1 was obtained by mixing the following emulsion with an aqueous solvent at the ratio shown in the table.
- Emulsion (EM-1) containing a composition (AD) having an acrylic resin (D) on the surface of metal oxide particles (a): 100 parts by weight - Melamine compound ("Beccamin" manufactured by DIC Corporation) (registered trademark) APM) (C-1): 20 parts by weight / Conductive compound (B-1): 25 parts by weight (solid content weight)
<Laminated polyester film>
Next, PET pellets containing substantially no particles (intrinsic viscosity 0.63 dl/g) were sufficiently vacuum-dried, then fed into an extruder, melted at 285°C, extruded into a sheet through a T-shaped nozzle, and allowed to stand still. It was wound around a mirror-finished casting drum with a surface temperature of 25° C. using an electric current casting method, and was cooled and solidified. This unstretched film was heated to 90° C. and stretched 3.4 times in the longitudinal direction to obtain a uniaxially stretched film (B film).

Next, coating composition 1 was applied to the corona discharge treated surface of the uniaxially stretched film using a bar coater. Both ends in the width direction of the uniaxially stretched film coated with the coating composition were held with clips and led to the preheating zone to bring the ambient temperature to 75°C. Subsequently, a radiation heater was used to bring the ambient temperature to 110°C, and then the ambient temperature was lowered to 110°C. The coating composition was dried at 90° C. to form a layer (X). Subsequently, the laminated polyester was continuously stretched 3.5 times in the width direction in a 120°C heating zone (stretching zone), and then heat treated for 20 seconds in a 230°C heat treatment zone (heat setting zone) to complete crystal orientation. Got the film. The thickness of the PET film measured by observing the cross section of the obtained laminated polyester film using a transmission electron microscope (TEM) was 50 μm, and the thickness of layer (X) was 1000 nm. The properties of the obtained laminated polyester film are shown in the table. It was excellent in initial surface resistivity, rate of change after one month, transparency, scratch resistance, and interference unevenness.

<Example 2>
A 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 properties of the obtained resin film are shown in the table.
<Coating composition>
The following emulsion was mixed with an aqueous solvent at the ratio shown in the table to obtain coating composition 2.
- Emulsion (EM-2) containing a composition (AD) having acrylic resin (D) on the surface of metal oxide particles (a): 100 parts by weight - Melamine compound ("Beccamin" manufactured by DIC Corporation) (registered trademark) APM) (C-1): 20 parts by weight / Conductive compound (B-1): 25 parts by weight (solid content weight)
<Example 3>
A 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 properties of the obtained resin film are shown in the table.
<Coating composition>
The following emulsion was mixed with an aqueous solvent at the ratio shown in the table to obtain coating composition 3.
- Emulsion (EM-3) containing a composition (AD) having acrylic resin (D) on the surface of metal oxide particles (a): 100 parts by weight - Melamine compound ("Beccamin" manufactured by DIC Corporation) (registered trademark) APM) (C-1): 20 parts by weight / Conductive compound (B-1): 25 parts by weight (solid content weight)
<Example 4>
A 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 properties of the obtained resin film are shown in the table.
<Coating composition>
Coating composition 4 was obtained by mixing the following emulsion in an aqueous solvent at the ratio shown in the table.
- Emulsion (EM-4) containing a composition (AD) having acrylic resin (D) on the surface of metal oxide particles (a): 100 parts by weight - Melamine compound ("Beccamin" manufactured by DIC Corporation) (registered trademark) APM) (C-1): 20 parts by weight / Conductive compound (B-1): 25 parts by weight (solid content weight)
<Example 5>
A 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 properties of the obtained resin film are shown in the table.
<Coating composition>
The following emulsion was mixed with an aqueous solvent at the ratio shown in the table to obtain coating composition 5.
- Emulsion (EM-5) containing a composition (AD) having acrylic resin (D) on the surface of metal oxide particles (a): 100 parts by weight - Melamine compound (“Beccamin” manufactured by DIC Corporation) (registered trademark) APM) (C-1): 20 parts by weight / Conductive compound (B-1): 25 parts by weight (solid content weight)
<Example 6>
A 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 properties of the obtained resin film are shown in the table.
<Coating composition>
The following emulsion was mixed with an aqueous solvent at the ratio shown in the table to obtain coating composition 6.
- Emulsion (EM-6) containing a composition (AD) having acrylic resin (D) on the surface of metal oxide particles (a): 100 parts by weight - Melamine compound (“Beccamin” manufactured by DIC Corporation) (registered trademark) APM) (C-1): 20 parts by weight / Conductive compound (B-1): 25 parts by weight (solid content weight)
<Example 7>
A 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 properties of the obtained resin film are shown in the table.
<Coating composition>
The following emulsion was mixed with an aqueous solvent at the ratio shown in the table to obtain coating composition 7.
- Emulsion (EM-7) containing a composition (AD) having acrylic resin (D) on the surface of metal oxide particles (a): 100 parts by weight - Melamine compound ("Beccamin" manufactured by DIC Corporation) (registered trademark) APM) (C-1): 20 parts by weight / Conductive compound (B-1): 25 parts by weight (solid content weight)
<Example 8>
A 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 properties of the obtained resin film are shown in the table.
<Coating composition>
Coating composition 8 was obtained by mixing the following emulsion with an aqueous solvent at the ratio shown in the table.
- Emulsion (EM-8) containing a composition (AD) having acrylic resin (D) on the surface of metal oxide particles (a): 100 parts by weight - Melamine compound ("Beccamin" manufactured by DIC Corporation) (registered trademark) APM) (C-1): 20 parts by weight / Conductive compound (B-1): 25 parts by weight (solid content weight)
<Example 9>
A 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 properties of the obtained resin film are shown in the table.
<Coating composition>
Coating composition 9 was obtained by mixing the following emulsion in an aqueous solvent at the ratio shown in the table.
- Emulsion (EM-2) containing a composition (AD) having acrylic resin (D) on the surface of metal oxide particles (a): 100 parts by weight - Melamine compound ("Beccamin" manufactured by DIC Corporation) (registered trademark) APM) (C-1): 40 parts by weight / Conductive compound (B-1): 25 parts by weight (solid content weight)
<Example 10>
A 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 properties of the obtained resin film are shown in the table.
<Coating composition>
The following emulsion was mixed with an aqueous solvent at the ratio shown in the table to obtain coating composition 10.
- Emulsion (EM-2) containing a composition (AD) having acrylic resin (D) on the surface of metal oxide particles (a): 100 parts by weight - Isocyanate compound (C-2): Daiichi Kogyo Seiyaku ( "Elastron" (registered trademark) E-37 (solid content concentration 28%, solvent: water): 20 parts by weight / Conductive compound (B-1): 25 parts by weight (solid content weight)
<Example 11>
A 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 properties of the obtained resin film are shown in the table.
<Coating composition>
Coating composition 11 was obtained by mixing the following emulsion with an aqueous solvent at the ratio shown in the table.
- Emulsion (EM-2) containing a composition (AD) having an acrylic resin (D) on the surface of metal oxide particles (a): 100 parts by weight - Carbodiimide compound ("Carbodilide" (registered trademark) manufactured by Nisshinbo) V-04B) (C-3): 20 parts by weight / Conductive compound (B-1): 25 parts by weight (solid weight)
<Example 12>
A 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 properties of the obtained resin film are shown in the table.
<Coating composition>
Coating composition 12 was obtained by mixing the following emulsion in an aqueous solvent at the ratio shown in the table.
- Emulsion (EM-9) containing a composition (AD) having acrylic resin (D) on the surface of metal oxide particles (a): 100 parts by weight - Melamine compound ("Beccamin" manufactured by DIC Corporation) (registered trademark) APM): 20 parts by weight / Conductive compound (B-1): 25 parts by weight (solid content weight)
<Example 13>
A resin film was obtained in the same manner as in Example 2, except that the thickness of layer (X) was changed to 80 nm. The properties of the obtained resin film are shown in the table.

<Example 14>
A 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 properties of the obtained resin film are shown in the table.
<Coating composition>
The following emulsion was mixed with an aqueous solvent at the ratio shown in the table to obtain coating composition 2.
・Emulsion (EM-2) containing a composition (AD) having acrylic resin (D) on the surface of metal oxide particles (a): 100 parts by weight ・Melamine compound (“Beccamin” manufactured by DIC Corporation) APM) (C-1): 10 parts by weight Carbodiimide compound (Nisshinbo Co., Ltd. "Carbodilide" (registered trademark) V-04B) (C-3): 10 parts by weight Conductive compound (B -1): 25 parts by weight (solid content weight)
<Example 15>
A 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 properties of the obtained resin film are shown in the table.
<Coating composition>
The following emulsion was mixed with an aqueous solvent at the ratio shown in the table to obtain coating composition 2.
- Emulsion (EM-2) containing a composition (AD) having acrylic resin (D) on the surface of metal oxide particles (a): 100 parts by weight - Isocyanate compound (C-2): Daiichi Kogyo Seiyaku ( "Elastron" (registered trademark) E-37 (solid content concentration 28%, solvent: water): 10 parts by weight, carbodiimide compound ("Carbodilide" (registered trademark) V-04B, manufactured by Nisshinbo Co., Ltd.) ( C-3): 10 parts by weight / Conductive compound (B-1): 25 parts by weight (solid weight)
<Example 16>
A 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 properties of the obtained resin film are shown in the table.
<Coating composition>
The following emulsion was mixed with an aqueous solvent at the ratio shown in the table to obtain coating composition 2.
- Emulsion (EM-2) containing a composition (AD) having acrylic resin (D) on the surface of metal oxide particles (a): 100 parts by weight - Isocyanate compound (C-2): Daiichi Kogyo Seiyaku ( "Elastron" (registered trademark) E-37 (solid content concentration 28%, solvent: water): 5 parts by weight, carbodiimide compound ("Carbodilide" (registered trademark) V-04B, manufactured by Nisshinbo Co., Ltd.) ( C-3): 15 parts by weight Conductive compound (B-1): 25 parts by weight (solid weight)
<Example 17>
The following emulsion was mixed with an aqueous solvent at the ratio shown in the table to obtain coating composition 2.
・Emulsion (EM-2) containing a composition (AD) having acrylic resin (D) on the surface of metal oxide particles (a): 100 parts by weight ・Melamine compound (“Beccamin” manufactured by DIC Corporation) (registered trademark) APM) (C-1): 20 parts by weight / Conductive compound (B-2): 25 parts by weight (solid content weight)
<Example 18>
The following emulsion was mixed with an aqueous solvent at the ratio shown in the table to obtain coating composition 2.
・Emulsion (EM-3) containing a composition (AD) having acrylic resin (D) on the surface of metal oxide particles (a): 100 parts by weight ・Melamine compound (“Beccamin” manufactured by DIC Corporation) (registered trademark) APM) (C-1): 20 parts by weight / Conductive compound (B-2): 25 parts by weight (solid content weight)
<Example 19>
The following emulsion was mixed with an aqueous solvent at the ratio shown in the table to obtain coating composition 2.
・Emulsion (EM-1) containing a composition (AD) having acrylic resin (D) on the surface of metal oxide particles (a): 100 parts by weight ・Melamine compound (“Beccamin” manufactured by DIC Corporation) (registered trademark) APM) (C-1): 20 parts by weight / Conductive compound (B-2): 25 parts by weight (solid content weight)
<Comparative example 1>
A 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 properties of the obtained resin film are shown in the table.
<Coating composition>
Coating composition 13 was obtained by mixing the following emulsion with an aqueous solvent at the ratio shown in the table.
- Emulsion (EM-2) containing a composition (AD) having acrylic resin (D) on the surface of metal oxide particles (a): 100 parts by weight - Melamine compound ("Beccamin" manufactured by DIC Corporation) Registered Trademark) APM) (C-1): 20 parts by weight <Comparative Example 2>
A 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 properties of the obtained resin film are shown in the table.
<Coating composition>
Coating composition 14 was obtained by mixing the following emulsion in an aqueous solvent at the ratio shown in the table.
- Acrylic resin (D-3): 100 parts by weight - Melamine compound (“Beccamin” (registered trademark) APM manufactured by DIC Corporation) (C-1): 20 parts by weight - Conductive compound (B-1): 25 parts by weight (solid weight)
<Comparative example 3>
A 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 properties of the obtained resin film are shown in the table.
<Coating composition>
Coating composition 15 was obtained by mixing the following emulsion in an aqueous solvent at the ratio shown in the table.
- Emulsion (EM-10) containing a composition (AD) having acrylic resin (D) on the surface of metal oxide particles (a): 100 parts by weight - Melamine compound ("Beccamin" manufactured by DIC Corporation) (registered trademark) APM) (C-1): 20 parts by weight / Conductive compound (B-1): 25 parts by weight (solid content weight)
<Comparative example 4>
A 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 properties of the obtained resin film are shown in the table.
<Coating composition>
The following emulsion was mixed with an aqueous solvent at the ratio shown in the table to obtain coating composition 16.
- Emulsion (EM-11) containing a composition (AD) having acrylic resin (D) on the surface of metal oxide particles (a): 100 parts by weight - Melamine compound (“Beccamin” manufactured by DIC Corporation) (registered trademark) APM) (C-1): 20 parts by weight / Conductive compound (B-1): 25 parts by weight (solid content weight)
<Comparative example 5>
A 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 properties of the obtained resin film are shown in the table.
<Coating composition>
Coating composition 17 was obtained by mixing the following emulsion with an aqueous solvent at the ratio shown in the table.
- Emulsion (EM-2) containing a composition (AD) having acrylic resin (D) on the surface of metal oxide particles (a): 100 parts by weight - Melamine compound ("Beccamin" manufactured by DIC Corporation) (registered trademark) APM) (C-1): 20 parts by weight / Conductive compound (B-1): 10 parts by weight (solid content weight)
<Comparative example 6>
A 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 properties of the obtained resin film are shown in the table.
<Coating composition>
Coating composition 18 was obtained by mixing the following emulsion with an aqueous solvent at the ratio shown in the table.
- Emulsion (EM-12) containing a composition (AD) having acrylic resin (D) on the surface of metal oxide particles (a): 100 parts by weight - Melamine compound (“Beccamin” manufactured by DIC Corporation) (registered trademark) APM) (C-1): 20 parts by weight / Conductive compound (B-1): 25 parts by weight (solid content weight)

In addition, in the table, "Y" represents "presence" and "N" represents "absence" regarding the presence or absence of the insulating phase (A) and the conductive phase (B). Further, in the table, E represents an index display; for example, "1.0E+07" represents "1.0×10 ⁷ ".

The present invention relates to a resin film that has both antistatic properties and scratch resistance, and whose antistatic properties hardly change depending on the environment. It can be suitably used as a plastic film used in the processing of various industrial products, particularly a hard coat film used in display applications, a hard coat film used in molding and decoration applications, and a base material for metal lamination.

Claims (8)

At least one surface has an insulating phase (A) and a conductive phase (B) measured by a conductivity measurement mode (conductive AFM) of an AFM (Atomic Force Microscope), and the insulating phase (A ) is a composition (AD) having an acrylic resin (D) on part or all of the surface of metal oxide particles (a) containing at least one metal element selected from the group consisting of Si, Al , and Zr . The metal oxide particles (a) have a number average particle diameter of 50 nm or more and 200 nm or less, and the conductive phase (B) is a polythiophene-based conductive compound (b) and an epoxy resin, a melamine resin, an oxazoline compound, When the surface α contains at least one crosslinking agent (c) selected from a carbodiimide compound and an isocyanate compound and has the insulating phase (A) and the conductive phase (B), the insulation on the surface α A resin film in which the area occupied by the phase (A) is 40% or more and 80% or less, and the surface resistivity of the surface α is 1.0×10 ¹⁰ Ω/□ or less.
However, the insulating phase (A) and the conductive phase (B) are specified by the following procedure.
First, the conductivity of the layer surface is measured by AFM under the following conditions.
[conditions]
Measuring device: Atomic force microscope (AFM) manufactured by Barker Corporation
Measurement mode: Conductive AFM (contact mode)
Cantilever: Bruker AXS SCM-PIC
(Material: Si, Spring constant K: 0.2 (N/m), Tip radius of curvature R: 20 (nm))
Measurement atmosphere: 23℃/in the air Measurement range: 1 (μm) Square resolution: 512 x 512
Cantilever movement speed: 10 (μm/s)
Maximum pushing load: 10 (nN)
Applied voltage: 10 (V)
After the measurement, select the "C-AFM Current" image and binarize the image displayed on the screen using "ScionImage" with a current value of 7.2 nA as the boundary value (maximum value: 10 nA, minimum value: 0 pA, threshold value 180 (black is 0, white is 255, and in a gray scale representing black to white in 256 steps, conductivity is set so that the area where 10 nA or more flows is 255 (white) and the area where 0 pA is 0 (black) An image is created, and in the resulting conductive image, areas with high current values represented by gray scale 180 or higher are white, and areas with low current values represented by gray scale less than 180 are black. Color-coded)) is used to form a conductive image on the surface, and in the conductive image, the black part is the insulating phase (A) and the white part is the conductive phase (B). The resin film according to claim 1, wherein the average domain diameter of the insulating phase (A) on the surface α is 50 nm or more and 200 nm or less. 3. The ratio _IB /IA of the conductivity IA of the insulating phase ( _A ) to the conductivity _IB of the conductive phase (B) on the surface _α is 100 or more and 100000 or less. resin film.
However, the above _IA and the above _IB are determined by the following method.
The conductivity of the layer surface is measured by AFM under the above conditions, and after the measurement, a conductivity image of the surface is obtained by the binarization.
The conductivity image is divided into 40 parts vertically and horizontally into 1600 regions of 25 nm x 25 nm, conductivity data is extracted for all areas where the entire area is solid black in the binarized image, and the average value is insulated. The conductivity of phase (A) is set as I _A , and the conductivity data is extracted for all areas where the entire area is solid white in the binarized image, and the average value is set as the conductivity _I of conductive phase (B). . The resin film according to any one of claims 1 to 3, wherein the haze change before and after the abrasion treatment on the surface α is 3.0% or less.
However, the abrasion treatment and the haze measurement are performed by the following method.
[Abrasion treatment]
The surface of the resin film is rubbed by moving #0000 steel wool back and forth 10 times at a load of 200 g/cm ² .
[Haze measurement]
This is done in accordance with JIS K 7136 "How to determine the haze of transparent materials" (2000 edition). The resin film according to any one of claims 1 to 4, wherein the elastic modulus (G _A ) of the insulating phase (A) on the surface α is 2000 MPa or more and 50000 MPa or less. Claims 1 to 5, wherein the ratio of the elastic modulus (G _A ) of the insulating phase (A) to the elastic modulus (G _B ) of the conductive phase (B), G _A /G _B , on the surface α is 4 or more and 20 or less. The resin film according to any one of. The resin film according to any one of claims 1 to 6, which is a laminate of two or more layers including a supporting base material and a layer (X) formed on the surface thereof . 8. The method for producing a resin film according to claim 1, wherein the coating composition (x) is applied to at least one side of the polyester film before crystal orientation is completed, and then stretched in at least one direction. A composition (AD) in which the coating composition (x) has an acrylic resin (D) on a part or all of the surface of the metal oxide particles (a), a polythiophene-based conductive material, A method for producing a resin film containing a compound (b) and at least one crosslinking agent (c) selected from an epoxy resin, a melamine resin, an oxazoline compound, a carbodiimide compound, and an isocyanate compound.

Images