阅读说明：本技术 树脂膜及其制造方法 (Resin film and method for producing same ) 是由 岩谷忠彦 阿部悠 坪仓翔 原田佳南 于 2019-08-30 设计创作，主要内容包括：本发明通过下述树脂膜,即至少一个表面具有由导电性AFM测得的绝缘相(A)和导电相(B),将上述具有绝缘相(A)和导电相(B)的表面设为表面α时,绝缘相(A)在上述表面α中所占的面积为40％以上、80％以下,上述表面α的表面电阻率为10～(10)Ω/□以下,从而提供兼具抗静电性和耐划痕性、抗静电性随环境的变化少(即稳定性优异)、且通过减少制造工序中的工序数从而可降低制造负荷的树脂膜。(The present invention provides a resin film having an insulating phase (A) and a conductive phase (B) on at least one surface thereof, wherein when the surface having the insulating phase (A) and the conductive phase (B) is defined as a surface α, the area of the insulating phase (A) in the surface α is 40% to 80%The surface resistivity of the surface α is 10 10 Omega/□ or less, and provides a resin film which has both antistatic properties and scratch resistance, shows little change in antistatic properties with the environment (i.e., has excellent stability), and can reduce the production load by reducing the number of steps in the production process.)

1. A resin film having at least one surface thereof an insulating phase (A) and a conductive phase (B) measured by an AFM (Atomic Force Microscope) conductivity measurement mode (conductive AFM), wherein when the surface having the insulating phase (A) and the conductive phase (B) is defined as a surface α, the area of the insulating phase (A) in the surface α is 40% or more and 80% or less, and the surface resistivity of the surface α is 1.0 × 10¹⁰Omega/□ or less.

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

3. Resin film according to claim 1 or 2, wherein the conductivity I of the insulating phase (a) in the surface a_AConductivity I with the conductive phase (B)_BRatio of (A to (B))_A/I_BIs 100 to 100000 inclusive.

4. The resin film according to any one of claims 1 to 3, wherein the haze change before and after the rubbing treatment of the surface a is 3.0% or less.

5. The resin film according to any one of claims 1 to 4, wherein the elastic modulus (G) of the insulating phase (A) in the surface a_A) Is 2000MPa or more and 50000MPa or less.

6. The resin film according to any one of claims 1 to 5, wherein the elastic modulus (G) of the insulating phase (A) in the surface a_A) Elastic modulus (G) with conductive phase (B)_B) Ratio G of_A/G_BIs 4 or more and 20 or less.

7. The resin film according to any one of claims 1 to 6, which is a laminate comprising 2 or more layers including a support base and a layer (X) formed on the surface of the support base.

8. The resin film according to any one of claims 1 to 7, 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, Fe.

9. The resin film according to any one of claims 1 to 8, wherein the conductive phase (B) contains a polythiophene-based conductive compound (B) and a crosslinking agent (c), and the crosslinking agent (c) is at least one selected from the group consisting of an epoxy resin, a melamine resin, an oxazoline compound, a carbodiimide compound, and an isocyanate compound.

10. The method for producing a resin film according to any one of claims 1 to 9, which comprises a step of applying the coating composition (x) to at least one surface of the polyester film before the completion of crystal orientation, and then performing stretching treatment and heat treatment in at least one direction,

the coating composition (x) contains a crosslinking agent (c) which is at least one selected from the group consisting of metal oxide particles (a), a conductive component (b), an epoxy resin, a melamine resin, an oxazoline compound, a carbodiimide compound and an isocyanate compound.

Technical Field

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

Background

Thermoplastic resin films, particularly biaxially oriented polyester films, have excellent properties such as mechanical properties, electrical properties, dimensional stability, transparency, and chemical resistance, and are therefore widely used in many applications such as magnetic recording materials and packaging materials. In particular, in recent years, in addition to carrier films in the processing steps of various industrial products, the quality required of polyester films has been increasing, such as various optical films for use in display members such as touch panels, liquid crystal display panels (LCDs), Plasma Display Panels (PDPs), and organic electroluminescence (organic EL). Under such circumstances, it is required to achieve both "antistatic properties" and "scratch resistance" for the purpose of suppressing damage and foreign matter in the production process and the processing process of a polyester film.

Antistatic property is imparted to suppress foreign matter defects caused by dust adhesion due to electrification. For example, patent document 1 describes a method of adding an antistatic agent to a polyester resin and coating the resulting mixture, and patent document 2 describes a method of coating a styrene sulfonic acid copolymer. As a practical problem, the antistatic property is often problematic due to changes in environment such as humidity, temperature, and elapsed time from the production in use.

On the other hand, the scratch resistance is provided for suppressing surface grinding due to contact with or sliding on the conveying roller during processing. For example, a hard coat film in which a layer (hard coat layer) made of an Ultraviolet (UV) curable resin is laminated is used, but in cutting, punching, or the like, workability for punching is required to be ensured so as not to cause cracking of the scratch resistant layer. If the workability is poor, there are problems that cracks are generated at the end portions to impair the design properties, or that chipping occurs to cause defects.

In response to these requirements, patent document 3 proposes a film obtained by mixing a conductive material into a hard coat layer, and patent document 4 proposes a laminated film in which a hard coat layer is further applied to the upper surface of an antistatic layer.

Documents of the prior art

Patent document

Patent document 1: japanese laid-open patent publication No. 61-204240

Patent document 2: japanese laid-open patent publication No. 7-101016

Patent document 3: japanese patent laid-open publication No. 2011-033658

Patent document 4: japanese patent laid-open No. 2008-176317

Disclosure of Invention

Problems to be solved by the invention

However, for example, the laminated films having an antistatic layer in patent documents 1 and 2 are insufficient in the effect of suppressing damage in the processing step. On the other hand, the techniques described in patent documents 3 and 4 can suppress damage. However, in patent document 3, both scratch resistance and antistatic property cannot be sufficiently achieved. In addition, the technique of patent document 4 has insufficient antistatic performance in a step after the hard coating process.

Accordingly, an object of the present invention is to provide a technique for stably mass-producing a resin film that achieves both antistatic properties and scratch resistance, while eliminating the above-mentioned drawbacks.

Means for solving the problems

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

(1) A resin film having at least one surface thereof an insulating phase (A) and a conductive phase (B) measured by an Atomic Force Microscope (AFM) conductivity measurement mode, the resin film having the insulating phase (A) and the conductive phase (B)(B) When the surface of (a) is a surface α, the area of the insulating phase (a) in the surface α is 40% to 80%, and the surface resistivity of the surface α is 10¹⁰Omega/port or less.

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

(3) The resin film according to (1) or (2), wherein the conductivity I of the insulating phase (A) in the surface α is_AConductivity I with the above-mentioned conductive phase (B)_BRatio of (A to (B))_A/I_BIs 100 to 100000 inclusive.

(4) The resin film according to any one of (1) to (3), wherein a haze change before and after the rubbing treatment in 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) of the insulating phase (A) in the surface α is_A) Is 2000MPa or more and 50000MPa or less.

(6) The resin film according to any one of (1) to (5), wherein the elastic modulus (G) of the insulating phase (A) in the surface α is_A) Elastic modulus (G) with conductive phase (B)_B) Ratio G of_A/G_BIs 4 or more and 20 or less.

(7) The resin film according to any one of (1) to (6), which is a laminate comprising 2 or more layers including a support base and a layer (X) formed on the surface of the support base.

(8) The resin film according to any one of (1) to (7), 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 resin film according to any one of (1) to (8), wherein the conductive phase (B) contains a polythiophene-based conductive compound (B) and a crosslinking agent (c), and the crosslinking agent (c) is at least one selected from the group consisting of an epoxy resin, a melamine resin, an oxazoline compound, a carbodiimide compound and an isocyanate compound.

(10) The method for producing a resin film according to any one of (1) to (9), which comprises a step of applying a coating composition (x) to at least one surface of the polyester film before completion of crystal orientation, and then performing stretching treatment and heat treatment in at least one direction,

the coating composition (x) contains a crosslinking agent (c) which is at least one selected from the group consisting of metal oxide particles (a), a conductive component (b), an epoxy resin, a melamine resin, an oxazoline compound, a carbodiimide compound and an isocyanate compound.

ADVANTAGEOUS EFFECTS OF INVENTION

The resin film of the present invention has both antistatic properties and scratch resistance, and the antistatic properties are less changed with the environment (i.e., excellent in stability), and the production load can be reduced by reducing the number of steps in the production process.

Drawings

Fig. 1 is a schematic view showing a conductivity distribution obtained by measuring the surface of the resin film of the present invention in a conductivity measurement mode (conductive AFM) by an AFM (Atomic Force Microscope). (in the actual measurement, the conductive images of 1 μm × 1 μm were divided into 40 parts along the vertical and horizontal directions, and into 1600 regions of 25nm × 25nm, and the schematic diagram shows the case where the conductive images of 1 μm × 1 μm were divided into 20 parts along the vertical and horizontal directions.)

Detailed Description

The resin film of the present invention will be described in detail below. The resin film of the present invention needs to have at least one surface having an insulating phase (a) and a conductive phase (B) measured by an Atomic Force Microscope (AFM) conductivity measurement mode, and when the surface having the insulating phase (a) and the conductive phase (B) is defined as a surface α, the area of the insulating phase (a) in the surface α is 40% to 80%, and the surface resistivity of the laminate film is 1 × 10¹⁰Omega/□ or less.

First, fig. 1 shows a schematic view of the distribution of the conductivity obtained by measuring the surface of the resin film of the present invention by a conductive AFM. As shown in fig. 1, the resin film of the present invention needs to have 2 regions having different physical properties on at least one surface. Specifically, when the surface is measured by the conductive AFM method, there are a region having relatively high conductivity (hereinafter referred to as a conductive phase (B)) and a region having relatively low conductivity (hereinafter referred to as an insulating phase (a)). As described later in detail, the image obtained by the conductive AFM measurement was binarized with "ScionImage" (maximum value: 10nA, minimum value: 0pA, threshold value 180 (in the gradation of black to 0, white to 255, and from black to white represented by 256 steps, the region through which 10nA or more flows was 255 (white), and the region through which 0pA flows was 0 (black), a conductive image was created, and in the conductive image obtained, the portion with a high current value represented by a tone of 180 or more was classified as white, and the portion with a low current value represented by a tone of less than 180 was classified as black)), and a conductive image was obtained. The obtained 1 μm × 1 μm conductive image was divided into 40 parts in the vertical and horizontal directions, and each of the 1600 regions was divided into 25nm × 25nm regions, and of the 1600 regions, 1 region was entirely pure black as an insulating phase (a), and 1 region was entirely pure white as a conductive phase (B). As a result of research conducted by the inventors of the present invention to solve the problems of the present invention, it was confirmed that many materials used for imparting antistatic properties are composed of a combination of polymers having low hardness and low molecular weight materials, and the properties thereof are easily changed by external stimuli such as pressure, temperature, humidity, and the like. In view of the above, it has been found that by providing an insulating phase (a) which is a region substantially free of an antistatic component on the film surface, both antistatic properties and scratch resistance can be achieved, and antistatic properties can be stabilized.

In the surface α, the insulating phase (a) occupies a desired proportion of the entire surface α. Specifically, the area occupied by the insulating phase (a) needs to be 40% to 80%. If the area occupied by the entire surface α is less than 40%, the antistatic performance may become unstable or the scratch resistance may be insufficient, and this is not practical. On the other hand, if the area occupied by the entire surface α exceeds 80%, antistatic performance is not sufficient, which is not preferable. The design of the conductive phase (B) and the insulating phase (a) can be adjusted by controlling the compatibility of the resin material, adjusting the coating and drying conditions, and by adjusting the amount and particle size of the filler when the filler is used. The specific methods for measuring the respective regions, and preferable coating compositions and methods for producing the same are as described below. A particularly preferable range of the area occupied by the insulating phase (a) on the entire surface α is 40% to 60%.

Next, the change in haze before and after the rubbing treatment of the surface α of the resin film of the present invention will be described. Here, the haze represents a value specified by JIS K7136 (2000), and the haze of the film is regarded as an index mainly representing the transparency of the film. When the film is damaged on the surface by the rubbing treatment, the transparency is lowered. Therefore, comparing the haze values before and after the rubbing treatment corresponds to evaluating the amount of surface damage caused by the rubbing treatment.

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 rubbing treatment under the conditions described later. If the amount exceeds 3.0%, the hardness of the coating film becomes insufficient, or sufficient film-forming properties are not obtained, or the formation of the insulating phase (a) described later becomes insufficient, and as a result, not only scratch resistance is insufficient, but also antistatic properties become unstable, and particularly antistatic properties tend to fluctuate under oxygen exposure conditions, and sufficient stability may not be obtained. The specific method of the rubbing treatment and the method of measuring the haze are as described below. Preferably, it is more preferably 2.5% or less, and further preferably 1.9% or less.

Further, the surface resistivity of the surface α of the resin film of the present invention needs to be 1 × 10¹⁰Omega/□ or less. The surface resistivity is a value obtained by a measurement method described later, and is an index representing the average conductivity of the surface of the resin film in a macroscopic range as compared with the measurement in the above-described AFM-based conductivity measurement mode. Surface resistivity exceeding 1 x 10¹⁰Ω/□, the ratio of the insulating phase (a) is too high, or the performance of the conductive phase (B) is insufficient, so that sufficient antistatic performance cannot be obtained. The method of measuring the surface resistivity is as described later. The surface resistivity is preferably 1X 10⁹Omega/□ or less, particularlyPreferably 1X 10⁷Omega/□ or less. On the other hand, the lower limit is not particularly limited, but is preferably 1 × 10 in a practical structure from the viewpoint of film formability and cost⁴Omega/□ or more.

[ 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, polyurethane resins, melamine resins, epoxy resins, and the like. In the present invention, acrylic resin and melamine resin are preferable from the viewpoint of stability when produced by a preferred production method described later.

The resin film in the present invention may be a single-layer film or a laminated film as long as at least one surface thereof has a surface α satisfying the above-described condition. It may have a layer formed on at least one side or both sides of the support substrate.

Here, the "layer" in the present invention means: and a portion having a finite thickness which is divided from the surface of the laminate in the thickness direction by a boundary surface in which the composition of the constituent elements, the shape of the inclusion such as particles, and the physical properties in the thickness direction of the adjacent portion are discontinuous. More specifically, it means: when the laminate is observed in a cross section in the thickness direction from the surface using various types of composition/element analyzers (FT-IR, XPS, XRF, EDAX, SIMS, EPMA, EELS, etc.), electron microscopes (transmission type, scanning type), or optical microscopes, the laminate is divided into regions having a limited thickness by the discontinuous boundary surfaces.

[ layer (X) ]

The resin film of the present invention preferably has a layer (X) on at least one surface of the support base material, the layer (X) being designed from the viewpoint of antistatic properties and scratch resistance, and the layer (X) preferably has the surface α. As the resin constituting the layer (X), those exemplified as the resin constituting the resin film described above can be preferably used. The method for forming the layer (X) is not particularly limited as long as the above conditions are satisfied, and it is preferably formed from a coating composition. The film coated with the coating composition described later may be produced in the process of forming the supporting substrate, or the coating composition may be applied to the supporting substrate, dried, and wound after the formation of the supporting substrate.

For example, when the layer (X) is formed by coating, the thickness of the layer (X) (the coating thickness after drying) is preferably 10 to 2000nm, more preferably 40 to 1000nm, and still more preferably 80 to 800 nm. When the thickness is 10nm to 2000nm, the layer (X) is preferable because the layer can provide the desired functions, i.e., antistatic properties, scratch resistance and coating film quality.

[ measurement of conductivity Using AFM ]

At least one surface of the resin film of the present invention is observed with the conductive phase (B) and the insulating phase (a) when measured by a conductive AFM. Here, the measurement of the conductivity by the atomic force microscope will be briefly described. The atomic force microscope is a means for measuring the shape of irregularities by scanning the shape of the surface using a cantilever having a sharp tip at the atomic level, and the generation of a weak current on the film surface can be detected and mapped (mapping) by applying a voltage between the cantilever and the sample using a cantilever having conductivity at the time of measurement. Such a measurement is referred to as a conductivity measurement mode or conductivity AFM (Conductive AFM: c-AFM). In the measurement of the conductive AFM, a minute current (tunnel current) that has oozed out across an insulating air layer can be detected, and a minute difference in conductivity (conductivity of the film surface) in a minute region directly below the cantilever can be efficiently detected. Details and measurement methods are as described later.

In the resin film of the present invention, the shape of the region formed by the insulating phase (a) in the surface α falls within a preferable range. Specifically, the average domain diameter of the insulating phase (a) in the surface α is preferably 50nm to 200nm, and particularly preferably 50nm to 100 nm. When the average domain diameter of the insulating phase (a) is less than 50nm, scratch resistance may be reduced and antistatic performance may be unstable. On the other hand, when the average domain diameter of the insulating phase (a) exceeds 200nm, the formation of a conductive path may be inhibited, and as a result, sufficient antistatic properties may not be obtained. As a method for controlling the average domain diameter, in the case where a metal oxide is used as a constituent material of the insulating phase (a) in a preferable coating composition described later, the particle diameter can be used for control.

[ conductivity I of the above conductive phase (B)_BAnd the conductivity I of the insulating phase (A)_A]

The current value (index of conductivity) obtained when the resin film of the present invention is measured by conductive AFM is in a preferable range of numerical values. Specifically, the conductivity I of the conductive phase (B)_BConductivity I with the insulating phase (A)_ARatio of (A to (B))_B/I_APreferably 100 to 100000, and particularly preferably 3000 to 100000. Ratio of electrical conductivities I_B/I_AIf it is less than 100, the above-mentioned separation structure between the insulating phase (a) and the conductive phase (B) may be insufficiently formed, and the scratch resistance may be insufficient and the antistatic performance may be unstable. On the other hand, the upper limit is not particularly limited, but is preferably 100000 or less. Details and measurement methods are as described later.

[ measurement of elastic modulus Using AFM ]

In addition, the surface α of the resin film of the present invention has a preferable numerical range of the elastic modulus measured by an atomic force microscope. Specifically, the elastic modulus G of the insulating phase (A)_APreferably 2000MPa to 50000MPa, and particularly preferably 5000MPa to 20000 MPa. If the pressure is less than 2000MPa, the scratch resistance described above may not be obtained, and the stability of the antistatic performance may not be obtained. On the other hand, if the pressure exceeds 50000MPa, the processability of the film may be deteriorated (for example, the film may be easily broken during processing).

In addition, the elastic modulus G of the insulating phase (A) is on the surface α of the resin film of the present invention_AElastic modulus G with conductive phase (B)_BRatio G of_A/G_BPreferred ranges also exist. Specifically, G_A/G_BPreferably 4 to 20, more preferably 6 to 16, and particularly preferably 8 to 12. G_A/G_BWhen the hardness is less than 4 and more than 20, the hardness of the resin film tends to be soft or hard, and thus it is difficult to achieve both scratch resistance and processabilityThe situation is.

In addition, in the surface α of the resin film of the present invention, the elastic modulus G of the conductive phase (B)_BPreferably 500MPa to 2000 MPa. If the pressure is less than 500MPa, the scratch resistance of the resin film may be reduced, and if the pressure exceeds 2000MPa, the processability may be reduced.

Here, the elastic modulus measurement by the atomic force microscope is a compression test using a probe of a very small portion, and is a degree of deformation caused by a pressing force, and therefore, the elastic modulus of the surface α and its spatial distribution can be measured using a cantilever having a known spring constant. Specifically, in the above-described measurement of conductivity, the elastic modulus information of each region can be obtained by measuring a force curve described later in each region detected as the conductive phase (B) or the insulating phase (a). In detail, as described in the example, the probe at the tip of the cantilever was brought into contact with the surface α using an atomic force microscope shown below, and the force curve was measured with a pressing force of 55nN, whereby the amount of deflection of the cantilever obtained was measured. In this case, the spatial resolution depends on the scanning range and the number of scanning lines of the atomic force microscope, but the lower limit is approximately 50nm under actual measurement conditions. Details and measurement methods are as described later.

[ supporting substrate, polyester film ]

As described above, the resin film of the present invention may be a single-layer film or a laminated film, and in a preferred embodiment, the resin film is formed by laminating a support base and a layer (X) having a surface α on at least one surface thereof. The resin used as the supporting base material is not particularly limited, and from the viewpoint of heat resistance and cost, polyester is exemplified. The support base is preferably a layer mainly composed of polyester (hereinafter, the layer mainly composed of polyester used as the support base is sometimes referred to as a polyester film). In the present invention, the main component means a component that accounts for 50% by weight or more of the entire resin constituting the layer.

In the present invention, the content of the particles in the supporting base material is preferably 0.1 wt% or less with respect to the entire supporting base material. When the content of the particles is within the above range, the internal haze can be 0.2% or less, and a resin film having 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, the polyester is a general term for polymers having ester bonds in the main chain, and it is preferable to use a polyester containing at least one component selected from ethylene terephthalate, trimethylene terephthalate, ethylene 2, 6-naphthalate, butylene terephthalate, trimethylene 2, 6-naphthalate, and α, β -bis (2-chlorophenoxy) ethane-4, 4' -dicarboxylic acid glycol.

The polyester film using the polyester is preferably a biaxially oriented polyester film. The biaxially oriented polyester film generally refers to the following polyester films: the polyester film is produced by stretching a polyester sheet or film in an unstretched state by about 2.5 to 5 times in the longitudinal direction and the width direction orthogonal to the longitudinal direction, respectively, and then subjecting the polyester sheet or film to a heat treatment to complete crystal orientation, and the polyester film exhibits a biaxially oriented pattern by wide-angle X-ray diffraction. When the polyester film is biaxially oriented, the polyester film has sufficient thermal stability, particularly dimensional stability and mechanical strength, and also has good planarity.

In addition, various additives such as an antioxidant, a heat stabilizer, a weather stabilizer, an ultraviolet absorber, an organic slipping agent, a pigment, a dye, organic or inorganic fine particles, a filler, an antistatic agent, a nucleating agent, and the like may be added to the polyester film to such an extent that the properties thereof are not deteriorated.

The thickness of the polyester film is not particularly limited, and may be suitably selected depending on the application and type, and is usually preferably 10 to 500 μm, more preferably 15 to 250 μm, and most preferably 20 to 200 μm in view of mechanical strength, handling properties, and the like. The polyester film may be a composite film obtained by coextrusion, or may be a film obtained by laminating the obtained films by various methods.

[ method for producing resin film ]

The method for producing a resin film of the present invention will be described below by way of examples, but the materials, the amounts used, the ratios, the processing contents, the processing steps, and the like described below may be appropriately modified as long as they do not depart from the gist of the present invention. Accordingly, 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 obtained by: the layer (X) is formed on the polyester film by applying a coating composition containing the metal oxide particles (a) and a binder component onto the polyester film and drying the solvent when the coating composition contains the solvent.

In the present invention, when the coating composition contains a solvent, it is preferable to use an aqueous solvent as the solvent (to prepare an aqueous coating agent). When an aqueous solvent is used as the solvent, the solvent can be prevented from being evaporated violently in the drying step, and not only a uniform composition layer can be formed, but also the composition is excellent in terms of environmental load.

The aqueous solvent is water or a mixture of water and a water-soluble organic solvent such as an alcohol such as methanol, ethanol, isopropanol or butanol, a ketone such as acetone or methyl ethyl ketone, or a glycol such as ethylene glycol, diethylene glycol or propylene glycol at an arbitrary ratio.

The method of aqueous coating of the metal oxide particles (a) and the binder component includes: a method in which the metal oxide particles (a) and the binder component contain a hydrophilic group such as a carboxylic acid or a sulfonic acid; a method for performing emulsion-liquefaction by using an emulsifier.

The coating method of the coating composition (x) onto the polyester film is preferably an in-line coating method. The in-line coating method is a method of coating in the production process of a polyester film. Specifically, the method refers to a method of coating at any stage from the start of melt extrusion of a polyester resin to the start of biaxial stretching, followed by heat treatment and rolling, and generally, the method is applied to any of an unstretched (unoriented) polyester film (a film) in a substantially amorphous state obtained by quenching after melt extrusion, a uniaxially stretched (uniaxially oriented) polyester film (B film) obtained by stretching in the longitudinal direction, and a biaxially stretched (biaxially oriented) polyester film (C film) before heat treatment obtained by further stretching in the width direction.

In the present invention, the following method is preferably employed: the coating composition is applied to any of the above-mentioned a and B films before the completion of crystal orientation, and then the polyester film is uniaxially or biaxially stretched and subjected to heat treatment at a temperature higher than the boiling point of the solvent to complete crystal orientation of the polyester film, and the layer (X) and the surface α are provided. According to this method, the film formation of the polyester film and the coating and drying of the coating composition (i.e., the formation of the layer (X)) can be performed simultaneously, and therefore, this method is advantageous in terms of production cost. Further, by stretching after coating, the aggregation state of the metal oxide particles (a) in the layer (X) can be controlled, and the area, the domain diameter, and the like of the insulating phase (a) can be designed, whereby scratch resistance and antistatic property can be improved.

Among them, a method in which the coating composition is applied to a film (B film) uniaxially stretched in the longitudinal direction, then stretched in the width direction, and heat-treated is excellent. This is because, compared with a method in which biaxial stretching is performed after coating an unstretched film, since the stretching step is performed once less, defects and cracks in the composition layer due to stretching are less likely to occur, and a composition layer excellent in transparency, smoothness, and antistatic properties can be formed.

Further, by providing the layer (X) by the in-line coating method and performing the stretching treatment after the coating composition is applied, the surface alignment of the metal oxide particles (a) can be promoted, and the metal oxide particles (a) can be promoted to be aggregates having anisotropy, and as a result, the shape of the insulating phase (a) of the layer (X) can be optimized, and the antistatic property can be exhibited, and the scratch resistance, the processability, and the stability of the antistatic property under the change with time and the change in humidity can be made good.

In view of the above-described advantages, the layer (X) in the present invention is preferably provided by an in-line coating method. Here, as a coating method of the coating composition on the polyester film, any known coating method, for example, a bar coating method, a reverse coating method, a gravure coating method, a die coating method, a knife coating method, and the like can be used.

In the present invention, the most preferable method for forming the layer (X) is a method in which a coating composition using an aqueous solvent is applied to a polyester film by an in-line coating method, and then dried and heat-treated. Further, a method of applying the coating composition on the uniaxially stretched B film in-line is more preferable. In the method for producing a resin film of the present invention, the drying may be performed at a temperature ranging from 80 to 130 ℃ in order to complete the removal of the solvent of the coating composition. In addition, in order to complete the heat curing of the coating composition to complete the formation of the layer (X) while completing the crystal orientation of the polyester film, the heat treatment may be performed at a temperature ranging from 160 to 240 ℃. By changing the temperature and time of the high-temperature heat treatment, the preferable elastic modulus of the insulating phase (a) and the conductive phase (B) can be adjusted, and the scratch resistance and the processability can be improved.

Next, a method for producing a resin film according to the present invention will be described by taking, as an example, a case where a polyethylene terephthalate (hereinafter, referred to as PET) film is used as a polyester film, but the method is not limited thereto. First, pellets of PET were sufficiently vacuum-dried, and then supplied to an extruder, melt-extruded at about 280 ℃ into a sheet, and cooled to solidify, thereby producing an unstretched (unoriented) PET film (a film). The film is stretched 2.5 to 5.0 times in the longitudinal direction by a roller heated to 80 to 120 ℃ to obtain a uniaxially oriented PET film (B film). The coating composition of the present invention adjusted to a predetermined concentration was applied to one side of the B film.

In this case, the coated surface of the PET film may be subjected to a surface treatment such as corona discharge treatment before coating. By performing surface treatment such as corona discharge treatment, the wettability of the coating composition to the PET film is improved, and the coating composition is prevented from being repelled, whereby a layer (X) having a uniform coating thickness can be formed. After coating, the end of the PET film was held by a jig, introduced into a heat treatment zone (preheating zone) at 80 to 130 ℃ and the solvent of the coating composition was dried. After drying, the sheet is stretched 1.1 to 5.0 times in the width direction. Then, a heat treatment region (heat-set region) of 160 to 240 ℃ is introduced, and heat treatment is performed for 1 to 30 seconds to complete crystal orientation.

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

The resin film of the present invention may have an intermediate layer between the layer (X) and the support substrate, and when the intermediate layer is provided, damage may occur in the film when the film having the intermediate layer laminated thereon is wound or in a subsequent step of providing the layer (X) of the present invention. Therefore, in the present invention, it is preferable that the layer (X) is directly laminated on the support base material.

The resin film of the present invention is not limited to the structure of the support base material, and examples thereof include the following: a monolayer comprising only a layer a; 2 kinds of 2-layer laminated structure which is the laminated structure of the A layer and the B layer; 2 kinds of 3-layer laminated structures, namely a laminated structure of a layer A, a layer B and a layer A; a laminated structure of layer A, layer B and layer C, namely a laminated structure of 3 types of 3 layers; and so on.

The method of laminating the support base material in the resin film of the present invention is not limited, and examples thereof include a lamination method by a coextrusion method, a lamination method by lamination, a method based on a combination thereof, and the like. When a laminate is produced, different resin compositions may be produced for the purpose of imparting different functions to the respective layers. For example, in the case of 2 types of 3-layer laminated structures, i.e., a laminated structure of a layer a/B/a, the following method is used: from the viewpoint of transparency, the layer B is composed of homopolyethylene terephthalate, and particles and the like are added to the layer a in order to impart slipperiness.

[ coating composition ]

The layer (X) in the resin film of the present invention is preferably produced by: the coating composition constituting the layer (X) is applied to at least one surface of a support substrate, and then heat-treated. Specifically, the coating composition may contain metal oxide particles, an acrylic resin, a binder resin, and a conductive compound. In addition, various additives may be contained in addition to the above-mentioned components. Hereinafter, preferred embodiments of the components contained in the coating composition will be described in detail.

[ Metal oxide particles (a) ]

In the resin film of the present invention, the insulating phase (a) preferably contains a metal oxideAnd (b) particles (a) of a metal oxide containing at least one metal element selected from the group consisting of Si, Al, Ti, Zr, Se, and Fe. By containing the metal oxide particles (a), a nano uneven structure can be formed on the surface layer of the resin film, and the resin film has good slidability and excellent scratch resistance. Specific examples of the metal oxide particles (a) used in the resin film of the present invention include silicon dioxide (silicon oxide) (SiO)₂) Alumina (Al)₂O₃) Titanium dioxide (TiO)₂) Zirconium dioxide (ZrO)₂) Selenium dioxide (SeO)₂) Iron oxide (Fe)₂O₃) Particles, and the like. These may be used alone or in combination of two or more.

In particular, titanium oxide (TiO) is used₂) Particles, alumina (Al)₂O₃) Particles, zirconium oxide (ZrO)₂) When the particles are the metal oxide particles (a), the interference unevenness of the resin film can be suppressed and the scratch resistance can be provided, which is preferable.

The metal oxide particles (a) used in the resin film of the present invention preferably have a particle diameter of 10 to 100nm because a denser nano uneven structure is formed on the surface of the resin film and the frictional force is dispersed, resulting in excellent scratch resistance. The particle size of the metal oxide particles (a) in the present invention means: particle size determined by Scanning Electron Microscopy (SEM) using the following method.

(method for determining particle diameter of Metal oxide particle (a))

A chip obtained by cutting in a direction perpendicular to the surface of the resin film was prepared using a microtome, and the cross section thereof was observed with a scanning transmission electron microscope (SEM) at 100000 × magnification and photographed. From the photograph of the cross section, the particle size distribution of the particles present in the film was determined using Image analysis software Image-Pro Plus (Roper, Japan). The sectional photograph was selected from different arbitrary measurement fields, and the diameters (equivalent circle diameters) of 200 or more particles arbitrarily selected from the sectional photograph were measured, and the particle diameter was plotted on the horizontal axis and the existence ratio of the particles on the vertical axis to obtain a volume-based particle size distribution. In the volume-based particle size distribution, the particle diameter on the horizontal axis is represented by a scale of 10nm apart from 0nm as a starting point, and the presence ratio of particles on the vertical axis is represented by the calculation formula "presence ratio is the total volume of the detection particles having the corresponding particle diameter/the total volume of all the detection particles". From the spectrum of the existence ratio of the particles obtained in the above manner, the particle diameter at the peak representing the maximum was read.

The metal oxide particles (a) used in the resin film of the present invention are more preferably a composition (AD) having an acrylic resin (D) on a part or all of the surfaces of the metal oxide particles (a). 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 a force is applied to the resin film, the force can be dispersed to the particles. As a result, the scratch resistance of the resin film can be improved. Further, the transparency of the resin film is also maintained, which is preferable.

In order to obtain a composition (AD) having an acrylic resin (D) on a part or all of the surface of the metal oxide particles (a), a method of surface-treating the metal oxide particles (a) described later with the acrylic resin (D) may be mentioned. Specifically, the following methods (i) to (iv) can be exemplified. In the present invention, the surface treatment refers to a treatment for adsorbing and adhering the acrylic resin (D) to all or a part of the surface of the metal oxide (a) having a specific element.

(i) A method in which a mixture obtained by mixing the metal oxide particles (a) and the acrylic resin (D) in advance is added to a solvent and then dispersed.

(ii) A method of adding the metal oxide particles (a) and the acrylic resin (D) to a solvent in this order to disperse them.

(iii) A method of dispersing the metal oxide particles (a) and the acrylic resin (D) in a solvent in advance and mixing the obtained dispersion.

(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.

The target effect can be obtained by any of these methods.

Further, as a device for performing dispersion, 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, a ring mill, a pin mill, or the like can be used.

In addition, as a dispersing method, the above device is used, and a rotating shaft is rotated at a peripheral speed of 5-15 m/s. The rotation time is 5-10 hours.

In addition, in view of improving dispersibility, it is more preferable to use dispersed beads such as glass beads in the dispersion. The diameter of the beads is preferably 0.05-0.5 mm, more preferably 0.08-0.5 mm, and particularly preferably 0.08-0.2 mm.

The mixing and stirring may be carried out by shaking the vessel by hand, by using a magnetic stirrer or a paddle, or by ultrasonic irradiation or vibration dispersion.

The presence or absence of adsorption and adhesion of the acrylic resin (D) to all or part of the surface of the metal oxide particle (a) can be confirmed by the following analysis method. The measurement object was centrifuged (rotation speed 3,0000rpm, separation time 30 minutes) using a Hitachi bench-type ultracentrifuge (manufactured by Hitachi Seisakusho Co., Ltd.: CS150NX), the metal oxide particles (a) (and the acrylic resin (D) adsorbed on the surfaces of the metal oxide particles (a)) were sedimented, and then the supernatant was removed, and the sediment was concentrated and dried. The concentrated and dried sediment was 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). When the presence of the acrylic resin (D) in an amount of 1 wt% or more based on 100 wt% of the total amount of the metal oxide particles (a) on the surface of the metal oxide particles (a) was confirmed, it was considered that the acrylic resin (D) was adsorbed and adhered to the surface of the metal oxide particles (a).

[ acrylic resin (D) ]

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

The acrylic resin (D) in the present invention preferably has a monomer unit (D) represented by the formula (1)₁) And a monomer unit (d) represented by the formula (2)₂) And a monomer unit (d) represented by the formula (3)₃) The resin of (4).

[ chemical formula 1]

(in the formula (1), R₁The radical represents hydrogen or methyl. N represents an integer of 9 to 34 inclusive. ).

[ chemical formula 2]

(in the formula (2), R₂The radical represents hydrogen or methyl. In addition, R₄And the group represents a group containing 2 or more saturated carbon rings. ).

[ chemical formula 3]

(in the formula (3), R₃The radical represents hydrogen or methyl. In addition, R₅The group represents a hydroxyl group, a carboxyl group, a tertiary amino group, a quaternary ammonium salt group, a sulfonic acid group, or a phosphoric acid group. )

Here, the acrylic resin (D) in the present invention preferably has a monomer unit (D) represented by the formula (1)₁) The resin of (4).

When an acrylic resin having a monomer unit in which n is less than 9 in formula (1) is used, the dispersibility of the metal oxide particles (a) in an aqueous solvent (details of the aqueous solvent are described later) becomes unstable. Make itWhen an acrylic resin having a monomer unit of which n is less than 9 in the formula (1) is used, the metal oxide particles (a) may be strongly aggregated in the coating composition, and in some cases, the metal oxide particles (a) may be precipitated in the aqueous solvent. As a result, the transparency of the resin film may be impaired, or the resin film may become a protrusion and cause a defect. On the other hand, since the acrylic resin having a monomer unit in which n in formula (1) exceeds 34 has a significantly reduced solubility in an aqueous solvent, aggregation of the acrylic resin is likely to occur in the aqueous solvent. Since the aggregate is larger than the wavelength of visible light, a resin film having good transparency may not be obtained, and interference unevenness may be deteriorated when a coating film is further laminated on the surface layer of the laminated film of the present invention. By using a monomer unit (d) having the formula (1) as described above₁) The resin according to (2), wherein the metal oxide particles (a) are dispersed in an aqueous solvent with a moderate interaction, and after drying, the plurality of metal oxide particles (a) have anisotropy, and are finely aggregated in the resin film on a nanometer scale level to form a non-circular insulating region on the surface of the resin film, so that exposure of the conductive material can be suppressed, and the resistance of the antistatic property to temporal changes can be improved.

In order to provide the acrylic resin (D) of the present invention with a monomer unit (D) represented by the formula (1)₁) It is necessary to use a (meth) acrylate monomer (d) represented by the following formula (4)₁') as starting material.

As the (meth) acrylic ester monomer (d)₁') is preferably a (meth) acrylate monomer represented by an integer of 9 to 34 inclusive in formula (4), more preferably a (meth) acrylate monomer of 11 to 32 inclusive, and still more preferably a (meth) acrylate monomer of 13 to 30 inclusive.

[ chemical formula 4]

(meth) acrylate monomer (d)₁') any (meth) acrylic acid in the formula (4) wherein n is 9 to 34 inclusiveThe ester monomer is not particularly limited, and specific examples thereof include decyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, 1-methyltrodecyl (meth) acrylate, hexadecyl (meth) acrylate, octadecyl (meth) acrylate, eicosyl (meth) acrylate, docosyl (meth) acrylate, ditetradecyl (meth) acrylate, and triacontyl (meth) acrylate, and dodecyl (meth) acrylate and tridecyl (meth) acrylate are particularly preferable. These may be used alone or in admixture of 2 or more.

The acrylic resin (D) in the present invention is a resin composition having a monomer unit (D) represented by the above formula (2)₂) The resin (c) is important.

When an acrylic resin having a monomer unit containing only 1 saturated carbon ring in the formula (2) is used, the function as a steric hindrance may become insufficient, and the metal oxide particles (a) may aggregate or settle in the coating composition, or the metal oxide particles (a) may settle in an aqueous solvent in some cases. As a result, the transparency of the resin film may be impaired, or the resin film may become a protrusion and cause a defect.

Since the aggregate has a wavelength longer than that of visible light, a resin film having good transparency may not be obtained. In order to provide the acrylic resin (D) of the present invention with a monomer unit (D) represented by the formula (2)₂) It is necessary to use a (meth) acrylate monomer (d) represented by the following formula (5)₂') as starting material.

As the (meth) acrylate monomer (d) represented by the formula (5)₂') may be exemplified by various cyclic structures such as a crosslinked fused ring type (a structure in which 2 or more rings are bonded to each other with 2 elements in common), a spiro ring type (a structure in which 2 cyclic structures are bonded to each other with 1 carbon element in common), and specifically, a compound having a bicyclic group, a tricyclic group, a tetracyclic group, and the like may be exemplified.

[ chemical formula 5]

Examples of the bicyclic group-containing (meth) acrylate include isobornyl (meth) acrylate, bornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, adamantyl (meth) acrylate, and dimethyladamantyl (meth) acrylate, and isobornyl (meth) acrylate is particularly preferable.

Further, the acrylic resin (D) in the present invention is preferably a resin having a monomer unit (D) represented by the above formula (3)₃) The resin of (4).

When an acrylic resin having a monomer unit in which R in the formula (3) is present is used₅When the group 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 following may be present: the compatibility of the acrylic resin in the aqueous solvent becomes insufficient, and the acrylic resin precipitates in the coating composition, and the metal oxide particles (a) aggregate or settle along with the precipitation, or the metal oxide particles (a) aggregate in the drying step.

Since the aggregate has a wavelength longer than that of visible light, a resin film having good transparency may not be obtained. In order to provide the acrylic resin (D) of the present invention with a monomer unit (D) represented by the formula (3)₃) It is necessary to use a (meth) acrylate monomer (d) represented by the formula (6)₃') as starting material.

As the (meth) acrylate monomer (d) represented by the formula (6)₃') the following compounds may be exemplified.

[ chemical formula 6]

Examples of the (meth) acrylate monomer having a hydroxyl group include monoesterified products of a polyhydric alcohol such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2, 3-dihydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and polyethylene glycol mono (meth) acrylate and (meth) acrylic acid, and compounds obtained by ring-opening polymerization of epsilon-caprolactone and the monoesterified products thereof, and 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate are particularly preferable.

Examples of the (meth) acrylate monomer having a carboxyl group include α, β -unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, fumaric acid, and maleic acid, and half-esters of hydroxyalkyl (meth) acrylates and acid anhydrides, and acrylic acid and methacrylic acid are particularly preferable.

Examples of the tertiary amino group-containing monomer include N, N-dialkylaminoalkyl (meth) acrylates such as N, N-dimethylaminoethyl (meth) acrylate, N-diethylaminoethyl (meth) acrylate, and N, N-dimethylaminopropyl (meth) acrylate, N-dialkylaminoalkyl (meth) acrylamides such as N, N-diethylaminoethyl (meth) acrylamide, and N, N-dimethylaminopropyl (meth) acrylamide, and N, N-dialkylaminoalkyl (meth) acrylamides such as N, N-dimethylaminoethyl (meth) acrylate are particularly preferable.

The quaternary ammonium salt group-containing monomer is preferably a monomer obtained by reacting a quaternizing agent such as an epihalohydrin, a halobenzyl group, or a haloalkyl group with the tertiary amino group-containing monomer, and specific examples thereof include (meth) acryloyloxyalkyltrialkylammonium salts such as 2- (methacryloyloxy) ethyltrimethylammonium chloride, 2- (methacryloyloxy) ethyltrimethylammonium bromide, and 2- (methacryloyloxy) ethyltrimethylammonium dimethylphosphate, and (meth) acryloyloxyalkyltrialkylammonium salts such as methacryloylaminopropyltrimethylammonium chloride and methacryloylaminopropyltrimethylammonium bromide, (meth) acrylic acid tetraalkylammonium salts such as tetrabutylammonium (meth) acrylate, and (meth) acrylic acid trialkylbenzylammonium (meth) acrylates such as trimethylbenzylammonium (meth) acrylate, 2- (methacryloyloxy) ethyltrimethylammonium chloride is particularly preferred.

Examples of the sulfonic acid group-containing monomer include (meth) acrylamido-alkanesulfonic acids such as butylacrylamide sulfonic acid and 2-acrylamido-2-methylpropanesulfonic acid, and sulfoalkyl (meth) acrylates such as 2-sulfoethyl (meth) acrylate, and 2-sulfoethyl (meth) acrylate is particularly preferable.

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

Among these, the acrylic resin (D) is preferably a monomer unit (D) having the formula (3) described above, particularly in view of having a high adsorption force with the metal oxide particles (a) described below and being capable of forming a stronger film₃) And R in the formula (3)₅The radical is hydroxyl or carboxyl.

In the present invention, the content of the acrylic resin (D) in the resin film is preferably 5 to 30% by weight, and when the content is within this range, the adsorption of the metal oxide particles (a) and the acrylic resin (D) becomes strong, 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 with respect to the entire resin film, and the content of the acrylic resin (D) in the resin film is more preferably 10% by weight or more and 30% by weight or less. In the present invention, the content of the resin film means the content of the solid content ([ (the weight of the coating composition) - (the weight of the solvent) ] of the coating composition forming the resin film.

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

[ Binder resin ]

The resin film and the layer (X) of the present invention preferably contain a binder resin as a component. The binder resin includes known acrylic resins, polyester resins, polyurethane resins, and copolymers thereof.

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

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

The polyisocyanate compound (I) is not particularly limited as long as it has 2 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 thereof (e.g., multimers (dimers, trimers, etc.), carbodiimide bodies, ketal bodies, allophanate bodies, uretdione bodies, polyamine-modified polyisocyanates, etc. ], and the like. The polyisocyanate compound (I) may be used alone or in combination of two or more. The aliphatic polyisocyanate is not particularly limited, and examples thereof include aliphatic diisocyanates [ e.g., alkane diisocyanates (e.g., C2-20 alkane diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, 2, 4-trimethylhexamethylene diisocyanate, dodecamethylene diisocyanate, lysine diisocyanate, 2-methylpentane-1, 5-diisocyanate, and 3-methylpentane-1, 5-diisocyanate, preferably C4-12 alkane diisocyanates) ], aliphatic polyisocyanates having 3 or more isocyanate groups (e.g., aliphatic tri-to hexaisocyanates such as 1,4, 8-triisocyanatooctane), and the like.

The alicyclic polyisocyanate is not particularly limited, and examples thereof include alicyclic diisocyanates { for example, cycloalkane diisocyanates (for example, C5-8 cycloalkane diisocyanate such as methyl-2, 4-or 2, 6-cyclohexane diisocyanate), isocyanatoalkyl cycloalkane isocyanates [ for example, isocyanatoC 1-6 alkylC 5-10 cycloalkane isocyanate such as 3-isocyanatomethyl-3, 5, 5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI) ], di (isocyanatoalkyl) cycloalkanes [ for example, di (isocyanatoC 1-6 alkyl) C5-10 cycloalkane such as hydrogenated xylylene diisocyanate ], di (isocyanatocycloalkyl) alkanes [ for example, hydrogenated diphenylmethane-4, bis (isocyanato group C5-10 cycloalkyl) C1-10 alkane such as 4 '-diisocyanate (4, 4' -methylenedicyclohexylisocyanate), polycycloalkane diisocyanate (norbornane diisocyanate or the like), and alicyclic polyisocyanates having 3 or more isocyanate groups (for example, alicyclic tri-to hexaisocyanates such as 1,3, 5-triisocyanatocyclohexane).

The araliphatic polyisocyanate is not particularly limited, and examples thereof include araliphatic diisocyanates { e.g., bis (isocyanatoc 1-6 alkyl) C6-12 aromatic hydrocarbons such as bis (isocyanatoalkyl) aromatic hydrocarbons [ e.g., Xylylene Diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI) (1, 3-or 1, 4-bis (1-isocyanato-1-methylethyl) benzene) ], araliphatic polyisocyanates having 3 or more isocyanato groups (e.g., araliphatic tri-to hexaisocyanates, etc.).

The aromatic polyisocyanate is not particularly limited, and examples thereof include aromatic diisocyanates { for example, aromatic hydrocarbon diisocyanates [ for example, C6-12 aromatic hydrocarbon diisocyanates such as o-, m-or p-phenylene diisocyanate, chlorobenzene diisocyanate, toluene diisocyanate, Naphthalene Diisocyanate (NDI) ], di (isocyanatoaryl) alkanes [ for example, diphenylmethane diisocyanate (MDI) (e.g., 2,4 ' -diphenylmethane diisocyanate, 4,4 ' -diphenylmethane diisocyanate), bis (isocyanato group C6-10 aryl) C1-10 alkane, etc. }, an aromatic polyisocyanate having 3 or more isocyanato groups (e.g., aromatic tri-to hexaisocyanate, such as 4,4 ' -diphenylmethane-2, 2 ', 5,5 ' -tetraisocyanate, etc.), and the like.

In the present invention, as the polyisocyanate compound (I), an alicyclic polyisocyanate is preferable in view of crack resistance.

The polyol (II) is not particularly limited as long as it has 2 or more hydroxyl groups.

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

The polyacrylic polyol is, for example, a copolymer having a (meth) acrylate unit and a unit derived from a component having a hydroxyl group (a component unit having a hydroxyl group), or the like. The polyacrylic polyol may have a unit other than the (meth) acrylate unit and the constituent unit having a hydroxyl group.

The polyester polyol is, for example, a copolymer having a polycarboxylic acid component unit and a polyol component unit. The polyester polyol may have units other than the polycarboxylic acid constituent unit and the polyol constituent unit.

The polyether polyol is, for example, a copolymer obtained by adding an alkylene oxide to a polyol. The polyol is not particularly limited, and for example, the above-mentioned diol and the like can be used. The polyhydric alcohols may be used alone or in combination of two or more.

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. The alkylene oxide 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 structural unit derived from the chain extender).

The chain extender is not particularly limited, and examples thereof include general chain extenders such as diols (e.g., C2-6 alkanediols such as ethylene glycol, 1, 4-butanediol, neopentyl glycol, and 1, 6-hexanediol), polyols (e.g., C2-6 alkanetriols such as glycerol, trimethylolpropane, and pentaerythritol), and diamines (e.g., ethylenediamine and hexamethylenediamine).

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

The resin film of the present invention preferably contains an ether component and a urethane component. When the resin film or layer (X) contains the urethane component and the ether component, the compatibility can be controlled, and when the resin film or layer (X) contains the metal oxide particles (a), the insulating phase (a) is easily formed on the surface of the resin film or layer (X). The method of incorporating the urethane component and the ether component into the resin film or layer (X) is not particularly limited, and a method using a urethane resin component having an ether bond is exemplified. Specifically, a polyurethane resin obtained by reacting a polyether polyol compound with an isocyanate compound is preferable. In the present invention, the ether-containing component means having an ether bond, and the urethane-containing component means having a urethane bond.

When such a urethane resin component is used, the hydrophilicity of the urethane resin component is improved. Therefore, when a coating composition (X) containing a composition (AD) comprising metal oxide particles (a) and/or an acrylic resin (D) on a part or all of the surface of the metal oxide particles (a) and a urethane resin component is applied to at least one surface of a polyester film serving as a support substrate and then heated to form a layer (X), the following phase separation structure can be formed: the polyurethane resin component having high hydrophilicity is biased toward the polyester film side as the base material layer in the layer (X), and the metal oxide particles (a) having low hydrophilicity and/or the composition (AD) having the acrylic resin (D) on a part or all of the surfaces of the metal oxide particles (a) is biased toward the vicinity of the surface of the layer (X). The phase separation structure in which the metal oxide particles (a) are localized near the surface of the layer (X) and the urethane resin component is localized near the interface between the layer (X) and the base material layer is preferable because a region (island component) having a high elastic modulus can be formed near the surface of the layer (X) and scratch resistance is exhibited, and the inner layer of the layer (X) exhibits processability due to relaxation of stress by the soft urethane resin component, and therefore scratch resistance and processability can be simultaneously achieved at a high level.

[ 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 for example, a Carbon-based material such as Carbon Nanotube (CNT), a polymer material having a conductive structure represented by a polythiophene structure, an acidic polymer in a free acid state, or the like can be used alone or in combination. From the viewpoint of initial characteristics of antistatic performance, a mixed component of a compound having a polythiophene structure and an acidic polymer in a free acid state is particularly preferable.

As the compound having a polythiophene structure, for example, a compound having a structure in which positions 3 and 4 of a thiophene ring are substituted, or the like can be used. Further, a compound in which oxygen atoms are bonded to carbon atoms at the 3-position and the 4-position of the thiophene ring can be preferably used. In the case of a compound in which a hydrogen atom or a carbon atom is directly bonded to the carbon atom, it may be difficult to make the coating liquid water-borne. The above-mentioned compounds can be produced by the methods disclosed in, for example, Japanese patent laid-open No. 2000-6324, European patent 602713 and U.S. Pat. No. 5391472, but methods other than these may be used.

For example, a composition in which a polythiophene such as poly (3, 4-ethylenedioxythiophene) is formed as a composite with an acidic polymer such as polystyrene sulfonic acid can be obtained by obtaining 3, 4-ethylenedioxythiophene using an alkali metal salt of 3, 4-dihydroxythiophene-2, 5-dicarboxylate as a starting material, and then introducing potassium persulfate, iron sulfate, and the previously obtained 3, 4-ethylenedioxythiophene into an aqueous polystyrene sulfonic acid solution to react with each other.

As the aqueous coating composition containing poly-3, 4-ethylenedioxythiophene and polystyrenesulfonic acid, those sold as "Baytron" P by h.c. starck (germany) and the like can be used.

On the other hand, examples of the acidic polymer in a free acid state include a polymeric carboxylic acid, a polymeric sulfonic acid, and a polyvinylsulfonic acid. Examples of the polymeric carboxylic acid include polyacrylic acid, polymethacrylic acid, and polymaleic acid. Further, as the polymeric sulfonic acid, for example, polystyrene sulfonic acid can be exemplified, and particularly, polystyrene sulfonic acid is most preferable from the viewpoint of antistatic property. It is noted that the free acid may take the form of a partially neutralized salt. In addition, the copolymer may be used in the form of being copolymerized with other copolymerizable monomers, for example, acrylic acid ester, methacrylic acid ester, styrene, and the like. The molecular weight of the polymeric carboxylic acid or polymeric sulfonic acid is not particularly limited, but the weight average molecular weight thereof is preferably 1000 to 1000000, more preferably 5000 to 150000, from the viewpoint of stability and antistatic property of the coating agent. The salt may be partially comprised of alkali salts such as lithium salt and sodium salt, ammonium salt, etc., within a range not impairing the characteristics of the invention. In the case of a salt in which the polyanion is neutralized, it is considered that the salt functions as a dopant. This is because the equilibrium of polystyrene sulfonic acid and ammonium salt, which function as very strong acids, is shifted to the acidic side by 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 film has a dense crosslinked structure, and therefore, the resin film is excellent in scratch resistance and stability of antistatic performance, which is preferable. Therefore, the conductive phase (B) of the resin film of the present invention preferably contains components derived from a melamine compound, an oxazoline compound, a carbodiimide compound, an isocyanate compound, and an epoxy compound.

In particular, when the coating composition (x) containing a melamine compound, an oxazoline compound, and a carbodiimide compound is used, it is preferable that the resin film contains a nitrogen-containing functional group, so that the polar power is improved, and the adhesiveness to a metal layer such as a coating layer, a sputtered layer, or a deposited layer is improved in the subsequent processing.

In addition, from the viewpoint of compatibility with conductivity, regarding the melamine compound, an increase in resistance value may be observed in the coexistence with a part of the conductive material, and therefore, it is preferable to use the coating composition (x) containing at least one selected from the group consisting of an oxazoline compound, a carbodiimide compound, and an isocyanate compound.

On the other hand, when optical characteristics such as transparency are required to be compatible, it is preferable to use two or more materials selected from crosslinking agents such as melamine compounds, oxazoline compounds, carbodiimide compounds, isocyanate compounds, and epoxy compounds in combination. By using two or more crosslinking agents in combination, the compatibility with the resin component can be easily provided by reducing the amount of the individual materials while maintaining the crosslinking properties required for improving the stability of conductivity and scratch resistance. Among them, it is preferable to use a coating composition (x) containing at least 2 selected from an oxazoline compound, a carbodiimide compound, and an isocyanate compound.

As the melamine-based compound, for example, there can be used: melamine; methylolated melamine derivatives obtained by condensing melamine with formaldehyde; compounds obtained by partial or complete etherification of methylolated melamine by reaction with lower alcohols; and mixtures thereof and the like. In particular, compounds having triazine and hydroxymethyl groups are particularly preferred. The melamine compound in the present invention refers to a component derived from a melamine compound when the following melamine compound forms a crosslinked structure with a polyurethane resin, an acrylic resin, an oxazoline compound, a carbodiimide compound, an isocyanate compound, an epoxy compound, or the like. The melamine compound may be any condensate formed from a monomer or dimer or more, or a mixture thereof. Examples of the lower alcohol used for the etherification include methanol, ethanol, isopropanol, n-butanol, and isobutanol. The resin is an imino methylated melamine resin, methylol methylated melamine resin, or a fully alkyl methylated melamine resin, and the resin has an imino group, a methylol group, or an alkoxymethyl group such as a methoxymethyl group or a butoxymethyl group as a group in 1 molecule. Among these, methylolated melamine resins are most preferred. In addition, in order to promote the thermal curing of the melamine compound, an acidic catalyst such as p-toluenesulfonic acid may be used.

When such a melamine compound is used, not only improvement in scratch resistance due to improvement in coating film hardness by self-condensation of the melamine compound is observed, but also reaction of the hydroxyl group and the carboxyl group contained in the acrylic resin with the melamine compound proceeds, and a firmer resin film and a film excellent in scratch resistance can be obtained.

The oxazoline compound refers to a component derived from an oxazoline compound described below, or a component in which an oxazoline compound forms a crosslinked structure with the urethane resin (D-2), the acrylic resin (D), the melamine compound, the isocyanate compound, the carbodiimide compound, or the like. The oxazoline compound is not particularly limited as long as it has an oxazoline group as a functional group in the compound, and is preferably a copolymer containing an oxazoline group, which is obtained by copolymerizing at least one other monomer and at least one kind of monomer containing an oxazoline group, with the inclusion of at least one or more oxazoline group-containing monomers.

Examples of the oxazoline group-containing monomer include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, and 2-isopropenyl-5-ethyl-2-oxazoline, and mixtures of 1 or 2 or more of these monomers may also be used. Among them, 2-isopropenyl-2-oxazoline is industrially readily available and is preferable.

The at least one other monomer used for the oxazoline-group-containing monomer in the oxazoline compound is not particularly limited as long as it is a monomer copolymerizable with the oxazoline-group-containing monomer, and examples thereof include acrylic esters or methacrylic esters such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate and 2-ethylhexyl methacrylate, unsaturated carboxylic acids such as acrylic acid, 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, vinyl esters such as vinyl acetate and vinyl propionate, vinyl esters such as methacrylic acid, and the like, Vinyl ethers such as methyl vinyl ether and ethyl vinyl ether, olefins such as ethylene and propylene, halogen-containing α, β -unsaturated monomers such as vinyl chloride, vinylidene chloride and vinyl fluoride, and α, β -unsaturated aromatic monomers such as styrene and α -methylstyrene, and mixtures of 1 or 2 or more of these may also be used.

The carbodiimide compound in the present invention refers to a component derived from a carbodiimide compound when the carbodiimide compound described below or a crosslinked structure of the carbodiimide compound with a urethane resin, an acrylic resin, a melamine compound, an isocyanate compound, an oxazoline compound, or the like. The carbodiimide compound is not particularly limited as long as it has 1 or 2 or more carbodiimide groups or an amino nitrile group in a tautomeric relationship with the carbodiimide group in the molecule as a functional group in the compound.

In the production of the carbodiimide compound, a known technique can be applied, and usually, the carbodiimide compound can be obtained by polycondensing a diisocyanate compound in the presence of a catalyst. As the diisocyanate compound which is a starting material of the carbodiimide compound, aromatic, aliphatic, alicyclic diisocyanate and the like can be used, and specifically, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexyl diisocyanate and the like can be used.

Examples

[ measuring method of characteristics and evaluation method of Effect ]

The method for measuring the characteristics and the method for evaluating the effects of the present invention are described below.

(1) Determination of surface alpha

(1-1) AFM-based surface α conductivity

For the measurement of the conductivity of the surface of the layer, analysis was performed using AFM (dimension icon, manufactured by Burker Corporation) and a conductivity measurement mode (conductivity AFM). Specifically, the measurement was carried out under the following conditions in accordance with the manual of conductive AFM. The sample was fixed by the following method to ensure conductivity from the layer surface to the sample stage. First, the resin film was cut into a size of 1cm × 1 cm. Next, the resin film was placed on a stainless steel sample table with the layer for measuring conductivity facing upward. Further, four sides of the resin film were fixed to a sample table so as to cover about 3mm from the end portion using a conductive tape (carbon double-sided tape for SEM (aluminum substrate, 8mm width) manufactured by shinsein EM corporation).

A measuring device: atomic Force Microscope (AFM) manufactured by Burker Corporation

Measurement mode: conductive AFM (conductive mode)

Cantilever: SCM-PIC manufactured by Bruker AXS

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

And (3) measuring atmosphere: at 23 ℃ in the atmosphere

Measurement range: 1 (mum) square

Resolution ratio: 512X 512

Cantilever moving speed: 10(μm/s)

Maximum press-in load: 10 (nN).

Voltage application: 10V

After the measurement, the "C-AFM Current" image was selected, and the image displayed on the screen was binarized by "ScionImage" (maximum value: 10nA, minimum value: 0pA, threshold value 180 (in the case where black is 0, white is 255, and the gray scale from black to white is represented by 256 steps, the region through which 10nA or more flows is 255 (white), and the region through which 0pA flows is 0 (black), a conductive image was prepared, and in the obtained conductive image, a portion having a high Current value represented by a tone of 180 or more was classified into white, and a portion having a low Current value represented by a tone of less than 180 was classified into black), to form a conductive image of the surface α. Note that the operation of performing the binarization processing according to the above steps corresponds to dividing the image into the insulating region and the conductive region with the current value of 7.2nA as a boundary value.

(1-2) Presence or absence of insulating phase (A) and conductive phase (B)

The conductive pattern of 1 μm × 1 μm obtained in (1-1) was divided into 40 parts in the vertical and horizontal directions, and each divided into 1600 regions of 25nm × 25 nm. In the 1600 regions, when all of 1 region is black and all of 1 region is white, the insulating phase (a) and the conductive phase (B) are included. That is, when an image including only the insulating phase (a) without a deviation in conductivity is obtained, an image including only the conductive layer (B) without a deviation in conductivity is obtained, or the size of any phase is less than 25nm square, it is determined that two phases of the insulating phase (a) and the conductive phase (B) are not present.

Further, the measurement range was arbitrarily selected and measured 10 times, and when the black portion and the white portion were observed 8 times or more, it was judged that the insulating phase (a) and the conductive phase (B) were present.

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

Of the 1600 regions of the conductive image obtained in (1-1), the conductivity data was extracted for all the regions in which the entire region of the binarized image was solid black, and the average value thereof was used as the conductivity (I) of the insulating phase (a)_A). Similarly, in 1600 regions of the conductive image obtained in (1-1), the elastic modulus was measured for all the regions in which all of the 1 regions were pure white, and the average value thereof was taken as the conductivity (I) of the conductive phase (B)_B). In addition, the measurement range was arbitrarily selected and 10 measurements were performed, and the average value of the total of 8 measurements excluding the maximum value and the minimum value was used.

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

The area ratio of the black portion was calculated as the area ratio of the insulating phase (a) using the analysis function of software (image processing software ImageJ/developer: National Institute of Health (NIH)) for the conductivity image obtained in (1-1) as a total occupied area ratio.

(1-5) average domain diameter of insulating phase (A)

For the conductivity image obtained in (1-1), the value of the radius calculated by using circle approximation using the analysis Particles function of software (image processing software ImageJ/developer: National Institute of Health (NIH)) was used as the average area diameter of the black portion. The data at the end of the measurement region was excluded from the measurement by validating the analysis on edges of analysis Particles.

(1-6) whether or not the insulating phase (A) contains the metal oxide (a)

The surface of the surface α was observed at a magnification of 10 ten thousand times using an SEM (scanning electron microscope), and elemental analysis by EDX (energy dispersive X-ray spectroscopy) was performed on the insulating phase (a) of the surface α on the polyester film to determine whether or not the metal oxide (a) was contained.

Specifically, the insulating phase (a) on the surface α observed by an electroluminescence scanning electron microscope (model S-4800) of hitachi high-tech System was subjected to element detection using a QUANTAX Flat QUAD System (model Xflash 5060FQ) of bruker axs, and when at least one metal element selected from the group consisting of Si, Al, Ti, Zr, Se, and Fe was detected, it was determined to have the metal oxide (a).

When 50% or more of the insulating phase (a) on the surface α contains the metal oxide (a), it is determined that the insulating phase (a) on the surface α contains the metal oxide (a).

(1-7) elastic modulus of AFM-based surface α

For the measurement of the surface elastic modulus of the layer surface, AFM (dimension icon manufactured by Burker Corporation) was used to perform the measurement in a peakfrceqnm mode, and the surface elastic modulus was determined from the obtained force curve by performing analysis based on JKR contact theory using attached analysis software "nanoscope analysis V1.40".

Specifically, first, the buckling sensitivity, spring constant, and tip curvature of the cantilever are configured according to the manual of the peakfrceqnm mode. The spring constant and the tip curvature vary depending on the individual cantilevers, and as a range not affecting the measurement, a cantilever satisfying the conditions of a spring constant of 0.1(N/m) to 0.4(N/m) and a tip curvature radius of 25(nm) or less is used for the measurement. The measurement conditions are as follows.

A measuring device: atomic Force Microscope (AFM) manufactured by Burker Corporation

Measurement mode: force curve acquisition using Ramp mode

Cantilever: SCM-PIC manufactured by Bruker AXS

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

And (3) measuring atmosphere: at 23 ℃ in the atmosphere

The number of times of measurement: 10 points

Cantilever moving speed: 10(μm/s)

Maximum press-in load: 10 (nN).

The assay used a Ramp mode. First, a place to be measured is determined from the conductive phase (B) and the insulating phase (a) obtained by the above-described conductivity measurement in the Scan mode, and the determined place is moved to the center of an image by the OFFSET. Subsequently, the mode is switched to the Ramp mode, and the force curve is acquired.

The resulting force curve was then analyzed using the analytical software "nanoscope analysis V1.40" to obtain the surface elastic modulus. The same measurement was repeated 10 times for each of the conductive phase (B) and the insulating phase (A), and the average value of the total of 8 times excluding the maximum value and the minimum value was used as the elastic modulus G of each phase_AAnd G_B。

(2) Scratch resistance

The occurrence of damage on the surface of the resin film after the rubbing treatment under the following conditions was confirmed by visual observation, and the following evaluation was performed.

[ Friction treatment]Steel Wool (BONSTAR #0000, manufactured by Nippon Steel Wool Co., Ltd.) was used for the surface of the resin film at 200g/cm²Is rubbed back and forth 10 times.

S: without damage

A: 1 to 5 lesions

B: 6 to 10 lesions

C: 11-15 lesions

D: more than 16 lesions.

(3-1) haze (transparency)

The haze was measured by leaving a sample of the resin film in a normal state (23 ℃ C., relative humidity 50%) for 40 hours, and then using a haze meter "NDH 5000" manufactured by Nippon Denshoku industries Co., Ltd., in accordance with JIS K7136 "method for determining the haze of a transparent material" (2000 edition). The measurement was performed by irradiating light from the surface side of the sample on which the surface α was laminated. 10 square samples each having 50mm sides were prepared, and the average value obtained by performing the measurement 1 time each and 10 times in total was used as the haze value of the sample.

(3-2) haze after Friction evaluation

After the rubbing treatment was performed in the same manner as in (2), the haze measurement was performed again by the above-described method.

(4) Interference spot

A black gloss tape (vinyl tape No.200-50-21, manufactured by YAMATO Co., Ltd.) was attached to the surface of the resin film opposite to the surface α so as not to intrude air bubbles.

The sample was placed in a dark room at a position 30cm directly below a 3-wavelength fluorescent lamp (3-wavelength daylight (F · L15 EX-N15W) manufactured by Panasonic corporation), and the degree of interference spots was visually observed while changing the viewing angle, and the following evaluation was performed. The case where B is greater than B is preferable.

A: substantially no interference spots are seen

B: slightly see the interference spot

C: the interference spot is strong.

(5) Antistatic Properties

(5-1) initial antistatic Property

Antistatic properties are determined by surface resistivity. The surface resistivity was measured by leaving the resin film to be measured under a condition of a relative humidity of 23% and a temperature of 25 ℃ for 24 hours, applying an applied voltage of 100V for 10 seconds under the atmosphere using a digital ultra-high resistance/micro-ammeter R8340A and a resistivity measuring box 12702A (manufactured by Advantest corporation, main electrode: Φ 50mm, counter electrode: Φ 103mm), and measuring. The unit is omega/□. The surface α of the sample was evaluated, and the average value obtained by 10 measurements in total was defined as the surface resistivity of the sample (R1).

1×10⁸Omega/□ or less is good, 1X 10¹⁰Below omega/□ is a practical level, exceeding 1X 10¹⁰The case of Ω/□ is a practically problematic level.

(5-2) antistatic Property after 1 month

After the resin film was produced, the film was stored in a state of being faced upward for 30 days under a relative humidity of 23% and 25 ℃ for the antistatic evaluation of the resin film, and then the evaluation was carried out by the same method as in (5-1). From the obtained values, the change rate with time (initial surface resistivity (Ω/□)/surface resistivity after 1 month (Ω/□) was obtained, and when the change rate with time was less than 3 times, it was good, and when it was less than 10 times, it was regarded as a practical level.

(5-3) antistatic Property when dried

Evaluation was performed in the same manner as in (5-1) except that after the production of the resin film, the film was allowed to stand at 105 ℃ and a relative humidity of 5% for 1 hour and then evaluated. (surface resistivity at the time of drying (Ω/□)/initial surface resistivity (Ω/□)) is preferably 1 or less, and a practical level is less than 5 times.

The properties and the like 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 composition (AD) having acrylic resin (D) on the surface of metal oxide particle (a)

100 parts by weight of isopropyl alcohol as a solvent was added to a conventional acrylic resin reaction vessel equipped with a stirrer, a thermometer and a reflux condenser, heated and stirred, and maintained at 100 ℃.

To this was added dropwise over 3 hours a mixture comprising: 40 parts by weight of eicosyl methacrylate with n ═ 19 as the (meth) acrylate (d' -1); 40 parts by weight of isobornyl methacrylate having 2 rings as the (meth) acrylate (d' -2); and 20 parts by weight of 2-hydroxyethyl acrylate as a (meth) acrylate (d' -3) having a hydroxyl group. After the completion of the dropwise addition, the mixture was heated at 100 ℃ for 1 hour, and then an additional catalyst mixture containing 1 part by weight of t-butyl peroxy-2-ethylhexanoate was added. Subsequently, it was heated at 100 ℃ for 3 hours and then cooled to obtain acrylic resin (D-1).

As the metal oxide particles (a), metal oxide particles containing Al element "NanoTek" Al were used₂O₃Slurry (C.I. Kasei CO., manufactured by LTD., number average particle diameter 60 nm: A-1), and "NanoTek" Al were sequentially added to an aqueous solvent₂O₃The slurry and the acrylic resin (D-1) were dispersed by the following method to obtain an emulsion (EM-1) containing a mixed composition (AD) of the metal oxide particles (a) and the acrylic resin (D-1). (method of the above (ii))

The addition amount ratio (weight ratio) of the metal oxide particles (a) and the acrylic resin (D-1) was 50/50 (note that the weight ratio was obtained by rounding off the 1 st position after the decimal point). The dispersion treatment was carried out using a homomixer and was carried out by rotating the homogenizer at a peripheral speed of 10m/s for 5 hours. In the finally obtained composition (BA), the weight ratio of the metal oxide particles (a) to the acrylic resin (B) was 50/50 (the weight ratio was determined by rounding off the 1 st position after decimal point).

The obtained composition (AD) was centrifuged by a hitachi bench ultracentrifuge (product of hitachi corporation: CS150NX) (rotation speed 3000rpm, separation time 30 minutes), the metal oxide particles (a) (and the acrylic resin (D) adsorbed on the surfaces of the metal oxide particles (a)) were sedimented, and then the supernatant was removed to concentrate the sediment and dry it. As a result of analyzing the precipitate after concentration and drying 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). That is, it was found that the acrylic resin (D) was adsorbed and adhered to the surface of the metal oxide particle (a) and the obtained composition (AD) was a particle having the acrylic resin (D) on the surface of the metal oxide particle (a).

< reference example 2>

An emulsion (EM-2) containing a composition (AD) having an acrylic resin (D) on the surface of a metal oxide particle (a)

EM-2 was obtained in the same manner as in reference example 1, except that the addition amount ratio (weight ratio) of the metal oxide particles (a) and the acrylic resin (D-1) was changed to (a)/(D-1): 60/40.

< reference example 3>

An emulsion (EM-3) containing a composition (AD) having an acrylic resin (D) on the surface of a metal oxide particle (a)

EM-3 was obtained in the same manner as in reference example 1, except that the addition amount ratio (weight ratio) of the metal oxide particles (a) and the acrylic resin (D-1) was changed to (a)/(D-1): 70/30.

< reference example 4>

An emulsion (EM-4) containing a composition (AD) having an acrylic resin (D) on the surface of a metal oxide particle (a)

Except that metal oxide particles containing Al element ("NanoTek" Al) are used as the metal oxide particles (a)₂O₃Slurry (c.i. kasei co., ltd. system, number average particle size 50 nm): a-2), and EM-4 was obtained in the same manner as in reference example 2.

< reference example 5>

An emulsion (EM-5) containing a composition (AD) having an acrylic resin (D) on the surface of a metal oxide particle (a)

Except that metal oxide particles containing Al element ("NanoTek" Al) are used as the metal oxide particles (a)₂O₃Slurry (c.i. kasei co., ltd., number average particle size 200 nm): EM-5 was obtained in the same manner as in reference example 2, except for A-3).

< reference example 6>

An emulsion (EM-6) containing a composition (AD) having an acrylic resin (D) on the surface of a metal oxide particle (a)

EM-6 was obtained in the same manner as in reference example 2, except that tin-antimony oxide particles (T-1 series (number average particle diameter: 60nm, manufactured by Mitsubishi Material Co., Ltd.): A-4) were used as the metal oxide particles (a).

< reference example 7>

An emulsion (EM-7) containing a composition (AD) having an acrylic resin (D) on the surface of a metal oxide particle (a)

Except that "Nanouse (registered trademark)" ZR (manufactured by Nissan chemical industries Co., Ltd., number average particle diameter of 90nm) containing Zr element was used as the metal oxide particles (a): EM-7 was obtained in the same manner as in reference example 2, except for A-5.

< reference example 8>

An emulsion (EM-8) containing a composition (AD) having an acrylic resin (D) on the surface of a metal oxide particle (a)

Except that "Snowtex (registered trademark)" colloidal silica slurry (manufactured by Nissan chemical industries, Ltd., number average particle diameter 80nm) containing an Si element was used as the metal oxide particles (a): EM-8 was obtained in the same manner as in reference example 2, except for A-6.

< reference example 9>

An emulsion (EM-9) containing a composition (AD) having an acrylic resin (D) on the surface of a metal oxide particle (a)

100 parts by weight of isopropyl alcohol as a solvent was added to a conventional acrylic resin reaction vessel equipped with a stirrer, a thermometer and a reflux condenser, and the mixture was heated and stirred and maintained at 100 ℃.

To this was added dropwise over 3 hours a mixture comprising: 40 parts by weight of eicosyl methacrylate with n ═ 19 as the (meth) acrylate (d' -1); 40 parts by weight of isobornyl methacrylate having 2 rings as the (meth) acrylate (d' -2); and 10 parts by weight of 2-hydroxyethyl acrylate and 10 parts by weight of 2,2, 2-trifluoroethyl propionate (d '-4) as the hydroxyl group-containing (meth) acrylate (d' -3). After the completion of the dropwise addition, the mixture was heated at 100 ℃ for 1 hour, and then an additional catalyst mixture containing 1 part by weight of t-butyl peroxy-2-ethylhexanoate was added. Subsequently, the mixture was heated at 100 ℃ 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 the acrylic resin (D-2) was used as the acrylic resin.

< reference example 10> production of acrylic resin (D-3)

100 parts by weight of water, 1 part by weight of polyethylene glycol monomethacrylate (the repeating unit of ethylene oxide is 16), and 0.5 part by weight of ammonium persulfate were added to a vessel 1 under a nitrogen atmosphere at normal temperature (25 ℃), and the mixture was heated to 70 ℃ to dissolve it, thereby obtaining a solution 1 at 70 ℃. Next, the following raw materials were added to the vessel 2 at the following ratio and stirred at room temperature (25 ℃ C.) to obtain a solution 2.

Then, 50 parts by weight of water was added to 100 parts by weight of solution 2 to obtain solution 3. Under a nitrogen atmosphere, the solution 1 was transferred to a reactor, and the solution 3 was continuously added dropwise to the solution 1 over 3 hours while maintaining the temperature of the solution in the reactor at 70 ℃. After the completion of the dropwise addition, the mixture was further stirred at 85 ℃ for 2 hours, then cooled to 25 ℃ and neutralized with aqueous ammonia to obtain an acrylic resin (D-3) emulsion.

< reference example 11>

An emulsion (EM-10) containing a composition (AD) having an acrylic resin (D) on the surface of a metal oxide particle (a)

EM-10 was obtained in the same manner as in reference example 1, except that the addition amount ratio (weight ratio) of the metal oxide particles (a) and the acrylic resin (D-1) was changed to (a)/(D-1): 20/80.

< reference example 12>

An emulsion (EM-11) containing a composition (AD) having an acrylic resin (D) on the surface of a metal oxide particle (a)

EM-11 was obtained in the same manner as in reference example 1, except that the addition amount ratio (weight ratio) of the metal oxide particles (a) and the acrylic resin (D-1) was changed to (a)/(D-1) of 80/20.

< reference example 13>

An emulsion (EM-12) containing a composition (AD) having an acrylic resin (D) on the surface of a metal oxide particle (a)

EM-12 was obtained in the same manner as in reference example 2, except that "Nanouse (registered trademark)" ZR ((20 nm number average particle diameter, manufactured by Nissan chemical industries, Ltd.): A-7) containing Zr element was used as the metal oxide particles (a).

< reference example 14> electroconductive compound B-1

To an aqueous solution of 1887 parts by weight containing 20.8 parts by weight of polystyrene sulfonic acid as an acidic polymer compound, 49 parts by weight of a 1% by weight aqueous solution of iron (III) sulfate, 8.8 parts by weight of 3, 4-ethylenedioxythiophene as a thiophene compound, and 117 parts by weight of a 10.9% by weight aqueous solution of peroxodisulfuric acid were added. The mixture was stirred at 18 ℃ for 23 hours. Then, 154 parts by weight of a cation exchange resin and 232 parts by weight of an anion exchange resin were added to the mixture, and after stirring for 2 hours, the ion exchange resin was filtered off to obtain an aqueous dispersion B-1 (solid content concentration of 1.3% by weight) comprising a mixture of poly (3, 4-ethylenedioxythiophene) and polystyrenesulfonic acid.

< reference example 15> electroconductive compound B-2

The ammonium salt of polystyrene sulfonic acid (weight-average molecular weight: 75,000) was diluted with water to obtain an aqueous solution B-2 of the ammonium salt of polystyrene sulfonic acid (solid content concentration: 5% by weight).

< example 1>

First, a coating composition 1 was prepared as follows.

< coating composition >

The following emulsions were mixed in an aqueous solvent at the ratios shown in the table to obtain a coating composition 1.

An emulsion (EM-1) containing the composition (AD) having the acrylic resin (D) on the surface of the metal oxide particle (a): 100 parts by weight

A melamine compound ("BECKAMINE" (registered trademark) APM manufactured by DIC corporation) (C-1): 20 parts by weight of

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

< laminated polyester film >

Subsequently, PET pellets (limiting viscosity of 0.63dl/g) substantially free of particles were sufficiently vacuum-dried, supplied to an extruder, melted at 285 ℃ and extruded into a sheet form from a T-shaped nozzle, and wound around a mirror casting drum having a surface temperature of 25 ℃ by an electrostatic casting method to be cooled and solidified. This unstretched film was heated to 90 ℃ and stretched 3.4 times in the longitudinal direction to prepare a uniaxially stretched film (film B).

Next, the coating composition 1 was applied to the corona discharge treated surface of the uniaxially stretched film by bar coating. Both widthwise ends of the uniaxially stretched film coated with the coating composition were held by a jig, introduced into a preheating zone to set an atmospheric temperature to 75 ℃, and then the coating composition was dried to form a layer (X) by using a radiation heater to set an atmospheric temperature to 110 ℃ and then an atmospheric temperature to 90 ℃. Subsequently, the polyester film was continuously stretched 3.5 times in the width direction in a heating zone (stretching zone) at 120 ℃ and then subjected to heat treatment in a heat treatment zone (heat-setting zone) at 230 ℃ for 20 seconds to obtain a laminated polyester film with completed crystal orientation. In the obtained laminated polyester film, the thickness of the PET film was 50 μm and the thickness of the layer (X) was 1000nm, as measured by observing the cross section with a Transmission Electron Microscope (TEM). The properties and the like of the obtained laminated polyester film are shown in the table. The initial surface resistivity, the rate of change after 1 month, the transparency, the scratch resistance, and the interference fringes were excellent.

< 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 described below. The properties and the like of the obtained resin film are shown in the table.

< coating composition >

The following emulsions were mixed in an aqueous solvent at the ratios shown in the table to obtain a coating composition 2.

An emulsion (EM-2) containing the composition (AD) having the acrylic resin (D) on the surface of the metal oxide particle (a): 100 parts by weight

A melamine compound ("BECKAMINE" (registered trademark) APM manufactured by DIC corporation) (C-1): 20 parts by weight of

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 described below. The properties and the like of the obtained resin film are shown in the table.

< coating composition >

The following emulsions were mixed in an aqueous solvent at the ratios shown in the table to obtain a coating composition 3.

An emulsion (EM-3) containing the composition (AD) having the acrylic resin (D) on the surface of the metal oxide particle (a): 100 parts by weight

A melamine compound ("BECKAMINE" (registered trademark) APM manufactured by DIC corporation) (C-1): 20 parts by weight of

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 described below. The properties and the like of the obtained resin film are shown in the table.

< coating composition >

The following emulsions were mixed in an aqueous solvent at the ratios shown in the table to obtain a coating composition 4.

An emulsion (EM-4) containing the composition (AD) having the acrylic resin (D) on the surface of the metal oxide particle (a): 100 parts by weight

A melamine compound ("BECKAMINE" (registered trademark) APM manufactured by DIC corporation) (C-1): 20 parts by weight of

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 described below. The properties and the like of the obtained resin film are shown in the table.

< coating composition >

The following emulsions were mixed in an aqueous solvent at the ratios shown in the table to obtain a coating composition 5.

An emulsion (EM-5) containing the composition (AD) having the acrylic resin (D) on the surface of the metal oxide particle (a): 100 parts by weight

A melamine compound ("BECKAMINE" (registered trademark) APM manufactured by DIC corporation) (C-1): 20 parts by weight of

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 described below. The properties and the like of the obtained resin film are shown in the table.

< coating composition >

The following emulsions were mixed in an aqueous solvent at the ratios shown in the table to obtain a coating composition 6.

An emulsion (EM-6) containing the composition (AD) having the acrylic resin (D) on the surface of the metal oxide particle (a): 100 parts by weight

A melamine compound ("BECKAMINE" (registered trademark) APM manufactured by DIC corporation) (C-1): 20 parts by weight of

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 described below. The properties and the like of the obtained resin film are shown in the table.

< coating composition >

The following emulsions were mixed in an aqueous solvent at the ratios shown in the table to obtain a coating composition 7.

An emulsion (EM-7) containing the composition (AD) having the acrylic resin (D) on the surface of the metal oxide particle (a): 100 parts by weight

A melamine compound ("BECKAMINE" (registered trademark) APM manufactured by DIC corporation) (C-1): 20 parts by weight of

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 described below. The properties and the like of the obtained resin film are shown in the table.

< coating composition >

The following emulsions were mixed in an aqueous solvent at the ratios shown in the table to obtain a coating composition 8.

An emulsion (EM-8) containing the composition (AD) having the acrylic resin (D) on the surface of the metal oxide particle (a): 100 parts by weight

A melamine compound ("BECKAMINE" (registered trademark) APM manufactured by DIC corporation) (C-1): 20 parts by weight of

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 described below. The properties and the like of the obtained resin film are shown in the table.

< coating composition >

The following emulsions were mixed in an aqueous solvent at the ratios shown in the table to obtain a coating composition 9.

An emulsion (EM-2) containing the composition (AD) having the acrylic resin (D) on the surface of the metal oxide particle (a): 100 parts by weight

A melamine compound ("BECKAMINE" (registered trademark) APM manufactured by DIC corporation) (C-1): 40 parts by weight of

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 described below. The properties and the like of the obtained resin film are shown in the table.

< coating composition >

The following emulsions were mixed in an aqueous solvent at the ratios shown in the table to obtain a coating composition 10.

An emulsion (EM-2) containing the composition (AD) having the acrylic resin (D) on the surface of the metal oxide particle (a): 100 parts by weight

Isocyanate compound (C-2): "ELASTRON" (registered trademark) E-37 (solid content: 28%, solvent: water) manufactured by first Industrial pharmaceutical Co., Ltd.: 20 parts by weight of

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 described below. The properties and the like of the obtained resin film are shown in the table.

< coating composition >

The following emulsions were mixed in an aqueous solvent at the ratios shown in the table to obtain a coating composition 11.

An emulsion (EM-2) containing the composition (AD) having the acrylic resin (D) on the surface of the metal oxide particle (a): 100 parts by weight

Carbodiimide Compound (Riqing "Carbodilite" (registered trademark) V-04B)

(C-3): 20 parts by weight of

Conductive compound (B-1): 25 parts by weight (solid content 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 described below. The properties and the like of the obtained resin film are shown in the table.

< coating composition >

The following emulsions were mixed in an aqueous solvent at the ratios shown in the table to obtain a coating composition 12.

An emulsion (EM-9) containing the composition (AD) having the acrylic resin (D) on the surface of the metal oxide particle (a): 100 parts by weight

A melamine compound (product of DIC corporation, "BECKAMINE" (registered trademark) APM): 20 parts by weight of

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 the layer (X) was changed to 80 nm. The properties and the like 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 described below. The properties and the like of the obtained resin film are shown in the table.

< coating composition >

The following emulsions were mixed in an aqueous solvent at the ratios shown in the table to obtain a coating composition 2.

An emulsion (EM-2) containing the composition (AD) having the acrylic resin (D) on the surface of the metal oxide particle (a): 100 parts by weight

A melamine compound ("BECKAMINE" (registered trademark) APM manufactured by DIC corporation) (C-1): 10 parts by weight

Carbodiimide-based Compound (Carbodilite (registered trademark) V-04B, Nisshin, Ltd.) (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 described below. The properties and the like of the obtained resin film are shown in the table.

< coating composition >

The following emulsions were mixed in an aqueous solvent at the ratios shown in the table to obtain a coating composition 2.

An emulsion (EM-2) containing the composition (AD) having the acrylic resin (D) on the surface of the metal oxide particle (a): 100 parts by weight

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

Carbodiimide-based Compound (Carbodilite (registered trademark) V-04B, Nisshin, Ltd.) (C-3): 10 parts by weight

Conductive compound (B-1): 25 parts by weight (solid content 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 described below. The properties and the like of the obtained resin film are shown in the table.

< coating composition >

The following emulsions were mixed in an aqueous solvent at the ratios shown in the table to obtain a coating composition 2.

An emulsion (EM-2) containing the composition (AD) having the acrylic resin (D) on the surface of the metal oxide particle (a): 100 parts by weight

Isocyanate compound (C-2): "ELASTRON" (registered trademark) E-37 (solid content: 28%, solvent: water) manufactured by first Industrial pharmaceutical Co., Ltd.: 5 parts by weight of

Carbodiimide-based Compound (Carbodilite (registered trademark) V-04B, Nisshin, Ltd.) (C-3): 15 parts by weight of

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

< example 17>

The following emulsions were mixed in an aqueous solvent at the ratios shown in the table to obtain a coating composition 2.

An emulsion (EM-2) containing the composition (AD) having the acrylic resin (D) on the surface of the metal oxide particle (a): 100 parts by weight

A melamine compound ("BECKAMINE" (registered trademark) APM manufactured by DIC corporation) (C-1): 20 parts by weight of

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

< example 18>

The following emulsions were mixed in an aqueous solvent at the ratios shown in the table to obtain a coating composition 2.

An emulsion (EM-3) containing the composition (AD) having the acrylic resin (D) on the surface of the metal oxide particle (a): 100 parts by weight

A melamine compound ("BECKAMINE" (registered trademark) APM manufactured by DIC corporation) (C-1): 20 parts by weight of

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

< example 19>

The following emulsions were mixed in an aqueous solvent at the ratios shown in the table to obtain a coating composition 2.

An emulsion (EM-1) containing the composition (AD) having the acrylic resin (D) on the surface of the metal oxide particle (a): 100 parts by weight

A melamine compound ("BECKAMINE" (registered trademark) APM manufactured by DIC corporation) (C-1): 20 parts by weight of

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 described below. The properties and the like of the obtained resin film are shown in the table.

< coating composition >

The following emulsions were mixed in an aqueous solvent at the ratios shown in the table to obtain a coating composition 13.

An emulsion (EM-2) containing the composition (AD) having the acrylic resin (D) on the surface of the metal oxide particle (a): 100 parts by weight

A melamine compound ("BECKAMINE" (registered trademark) APM manufactured by DIC corporation) (C-1): 20 parts by weight of

< 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 described below. The properties and the like of the obtained resin film are shown in the table.

< coating composition >

The following emulsions were mixed in an aqueous solvent at the ratios shown in the table to obtain a coating composition 14.

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

A melamine compound ("BECKAMINE" (registered trademark) APM manufactured by DIC corporation) (C-1): 20 parts by weight of

Conductive compound (B-1): 25 parts by weight (solid content 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 described below. The properties and the like of the obtained resin film are shown in the table.

< coating composition >

The following emulsions were mixed in an aqueous solvent at the ratios shown in the table to obtain a coating composition 15.

An emulsion (EM-10) containing the composition (AD) having the acrylic resin (D) on the surface of the metal oxide particle (a): 100 parts by weight

A melamine compound ("BECKAMINE" (registered trademark) APM manufactured by DIC corporation) (C-1): 20 parts by weight of

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 described below. The properties and the like of the obtained resin film are shown in the table.

< coating composition >

The following emulsions were mixed in an aqueous solvent at the ratios shown in the table to obtain a coating composition 16.

An emulsion (EM-11) containing the composition (AD) having the acrylic resin (D) on the surface of the metal oxide particle (a): 100 parts by weight

A melamine compound ("BECKAMINE" (registered trademark) APM manufactured by DIC corporation) (C-1): 20 parts by weight of

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 described below. The properties and the like of the obtained resin film are shown in the table.

< coating composition >

The following emulsions were mixed in an aqueous solvent at the ratios shown in the table to obtain a coating composition 17.

An emulsion (EM-2) containing the composition (AD) having the acrylic resin (D) on the surface of the metal oxide particle (a): 100 parts by weight

A melamine compound ("BECKAMINE" (registered trademark) APM manufactured by DIC corporation) (C-1): 20 parts by weight of

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 described below. The properties and the like of the obtained resin film are shown in the table.

< coating composition >

The following emulsions were mixed in an aqueous solvent at the ratios shown in the table to obtain a coating composition 18.

An emulsion (EM-12) containing the composition (AD) having the acrylic resin (D) on the surface of the metal oxide particle (a): 100 parts by weight

A melamine compound ("BECKAMINE" (registered trademark) APM manufactured by DIC corporation) (C-1): 20 parts by weight of

Conductive compound (B-1): 25 parts by weight (solid content weight) [ Table 1]

[ Table 2]

[ Table 3]

[ Table 3]

In the table, in the presence or absence of the insulating phase (a) and the conductive phase (B), "Y" represents "presence" and "N" represents "absence". In the table, E represents an index, for example, "1.0E + 07" means "1.0X 10⁷”。

Industrial applicability

The present invention relates to a resin film having both antistatic properties and scratch resistance, and the antistatic properties are less likely to change with the environment. Can be suitably used as a plastic film used for processing various industrial products, particularly as a hard coat film used for display applications, a hard coat film used for molding decoration applications, and a substrate for metal lamination.