JP2014235196A - Light-shielding film and method for producing the same, and focal plane shutter blade using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a light-shielding film which is used for a focal plane shutter blade of a digital single-lens reflex camera, and is excellent in light-shielding properties, low reflectivity, slidability, conductivity, heat resistance and resistance to high temperature and high humidity, and shock resistance, and to provide a method for producing the same.SOLUTION: A light-shielding film has an Ni-based metal film (B) which is formed of a crystal phase with a film thickness of 40-250 nm on both surfaces of a resin film (A), and has an Ni-based metal oxide film (C) with a film thickness of 100-400 nm on the outermost surface thereof. Both of arithmetic average heights Ra on the outermost surface is 0.1-2.1 μm, a minimum optical density in a wavelength of 380-780 nm as an index of light-shielding properties exceeds 4, a maximum regular reflectance is less than 0.4%, bending rigidity is 2.0 N m/m, a tear strength is 6.0 N/mm or more, and a coefficient of dynamic friction is 0.2 or less.

Description

  The present invention relates to a light shielding film, a method for producing the same, and a focal plane shutter blade using the same, and more specifically, a light shielding property required as a shutter blade material for use as a focal plane shutter blade of a high-speed digital single lens reflex camera. , Low-reflection, slidability, electrical conductivity, heat resistance, high temperature and high humidity resistance, low cost, impact resistance and durability, light-shielding film, manufacturing method thereof, and focal plane using the same Related to shutter blades.

  In recent years, high-speed (mechanical) shutters for digital cameras have been actively developed. This is because if the shutter speed is increased, a very high-speed subject can be photographed without blur and a clear image can be obtained. In general, a shutter opens and closes by rotating and moving a plurality of blades called shutter blades. To increase the shutter speed, the shutter blades need to operate and stop in a very short time. Therefore, weight reduction and high slidability are required. In addition, the shutter blades must have high mechanical characteristics that do not break, bend, or break due to contact between the blades or contact with its peripheral members when operating and stopping at high speed. Yes.

  In particular, the shutter speed of a digital single-lens reflex camera is required to be further increased due to the improvement of the continuous shooting function and the demand for new image expression, and the mechanical characteristics of the shutter blades are one of the important parameters. Further, when the shutter is closed, the shutter blades have a role of blocking light by covering the front surface of a photosensitive material such as a film or an image pickup device such as a CCD or CMOS, and needs to be completely shielded from light. . In addition, since the shutter blades generally have a structure in which a plurality of shutter blades overlap each other, leakage light is generated when the maximum regular reflectance of each blade surface is high, resulting in imaging defects. In order to prevent this, it is desired that the color of the blade material is black and the maximum regular reflectance on the blade surface is low.

  In general, a focal plane shutter installed immediately before a photosensitive material is used in a shutter unit for use in a digital single-lens reflex camera. The operation principle of the focal plane shutter is that the shutter opening / closing time is controlled by the travel of two light-shielding shutter curtains, and the exposure time is adjusted. . In recent focal plane shutter units, instead of a shutter curtain, a plurality of 4 to 5 shutter blades are each rotatably attached to an arm via a caulking pin. The plurality of shutter blades travel at a high speed along the surface of the substrate according to the movement of the arm, and perform an opening / closing operation of an opening provided in the substrate.

As an example of the material of such a focal plane shutter blade, for example, as shown in Patent Document 1, a metal plate material such as an aluminum alloy whose both surfaces of the base material are blackened with a hard carbon film can be used. Since an inexpensive material is generally used for the metal plate, the cost can be suppressed. Further, since the metal plate material has a high mechanical characteristic value, it can sufficiently withstand the impact at the time of starting and stopping accompanying the increase in speed. However, when using a metal plate as a base material, the specific gravity of the shutter blade is high and heavy, so not only high power consumption is required to drive the blade material, but also the sliding of the blade during high-speed operation and There is a problem that the vibration of the blade material immediately after the stop becomes extremely large.
Although metal plate materials are still used for low-speed shutter blades and a part of high-speed shutter blades, they are difficult to use for further speeding up due to the above problems.

In order to increase the shutter speed, a lighter product has been proposed that uses a resin film instead of a metal plate as the base of the focal plane shutter blade.
For example, Patent Document 2 proposes a light-shielding film in which a black PET film impregnated with a black pigment such as carbon black is used as a base material and a light-shielding layer containing carbon black or the like in a matrix resin is formed on both surfaces thereof. However, in such a light-shielding film, the thickness of the light-shielding layer must be several μm to several tens of μm in order to exhibit light shielding properties. The thickness of the shutter unit of the camera is limited, and in order to obtain a light-shielding film thickness that meets market demands, it is necessary to reduce the thickness of the black PET film as the base material. In the case of such a film structure, the mechanical properties of the entire film are mostly the properties of the black PET film of the base material. Therefore, when the base material becomes thin, the mechanical properties of the film cannot be obtained sufficiently, and the bending rigidity is particularly high. It may not be enough. When such a material with low bending rigidity is used for the focal plane shutter blades of a digital single lens reflex camera for further speedup, the film end face when it collides with pins or peripheral parts that fix the blade material when sliding. It has a problem that it is damaged from the part and inferior in durability and impact resistance for a long time.

In addition, even if it is not damaged when colliding with a pin or a peripheral part, when such a shutter blade with low bending rigidity is incorporated, the shutter blade undulates when suddenly sliding and stopping when the shutter is ON or OFF, The phenomenon of undulation occurs. If the next shutter is released when this undulation is occurring on the shutter blade, the blade may interfere with other blades and other peripheral components, causing damage and failure to move. I have it.
At present, this structure is most often used as a shutter blade for high speed, but due to the above-mentioned problems, the service speed has reached its limit and it is difficult to use it for further speedup.

  The present applicant has proposed a heat-resistant light-shielding film comprising a Ni-based metal film and a Ni-based oxide film on a resin film substrate in Patent Document 3. Here, by using a resin having a heat resistance of 200 ° C. or higher, such as polyimide or aramid, as the resin base material, it is exposed to a high-temperature environment during use or manufacturing, such as a light adjustment blade of a liquid crystal projector. However, it is now possible to provide a light-shielding film that does not cause deterioration of characteristics due to thermal effects. However, since such a use does not require a particularly high speed operation, there is no particular mention regarding strength characteristics. If a film with low mechanical strength is used to produce a focal plane shutter blade for a digital single-lens reflex camera for high-speed operation, as in the above example, pins and peripheral parts that fix the blade material when sliding When it collides, it will be damaged from the film end face part, and long-term durability and impact resistance will not be exhibited.

  On the other hand, in Patent Document 4 and Patent Document 5, a focal plane using a plurality of prepreg sheets in which glass fibers or carbon fibers are included in a matrix resin such as an epoxy resin or a polyurethane resin in order to reduce weight and improve bending rigidity. A light shielding film for a shutter blade material is disclosed. The light-shielding blade made of such a resin film is lightweight, has high bending rigidity, and has a very small undulation of the blade during sliding and immediately after stopping even at a high shutter speed of 1/8000 seconds. For this reason, even if a plurality of shutter operations are continuously performed, there is little possibility that the shutter blades interfere with each other, or the blades are damaged by colliding with the peripheral parts, and the shutter operation is not possible. Durability can be realized.

  However, since the light-shielding blade made of a prepreg sheet containing carbon fiber is very expensive, it is currently limited to being mounted only on models requiring high specifications. The light-shielding blade made of prepreg sheet containing glass fiber was developed by reducing the cost of prepreg sheet containing carbon fiber, and can be manufactured at about half the cost, but it is still cheap. For this reason, it is still difficult to mount a shading blade composed of a prepreg sheet containing carbon fiber or glass fiber in a low-priced zone that is a volume zone. Furthermore, the prepreg sheet containing these fibers is produced by temporarily molding individual prepreg sheets and then press-molding a plurality of prepreg sheets, so that the process is diverse and complicated. There's a problem. Therefore, digital SLR cameras in the volume zone use either low-strength light-shielding blades made of resin, or all light-shielding blades made of metal with high specific gravity, which has high bending rigidity but is disadvantageous for high-speed running. For the focal plane shutter blades or for some of the focal plane shutter blades that require the most impact resistance during sliding.

  Furthermore, the resin film containing glass fiber or carbon fiber has a large variation in the thickness of the individual prepreg sheets to be laminated. In this case, glass fibers or carbon fibers may fluff like burrs at the end face portion, and there is a problem that the quality control takes time, the defect rate is high, and the cost is further increased. Nonuniform thickness causes variations in mechanical strength and flatness, and conspicuous fibers such as burr on the end face cause uneven exposure when slit exposure is performed, leading to deterioration of image quality. . Also, under a constant curtain speed, the shutter speed can be increased by narrowing the distance between the two shutter blades. However, the resin film containing glass fiber or carbon fiber has burr on the end face. As a result, the slit interval cannot be narrowed, the exposure time is limited, and there is a problem that the shutter speed cannot be further increased.

Carbon fiber reinforced plastics, although the supply-demand balance is stable at present, is expected to continue to expand in the future, and may become a problem in the future in terms of stable supply. Because of these problems, the fiber-containing shutter blades have cleared the mechanical characteristics, but are limited to mounting on only a few models that require high specifications due to high cost.
Under such circumstances, there is a need for a light-shielding film that can achieve cost reduction while having mechanical properties equivalent to those of a fiber-containing shutter blade.

Japanese Patent Laid-Open No. 2-116837 JP 2009-271547 A Japanese Patent No. 5114995 JP 2008-299106 A JP 2000-75353 A

  Accordingly, an object of the present invention is to provide a light shielding property, low reflectivity, sliding property, conductivity, heat resistance, high temperature resistance and high humidity resistance required as a shutter blade material for use as a focal plane shutter blade of a high-speed digital single lens reflex camera. It is providing the light-shielding film which satisfy | fills, and the impact resistance and durability which are cheap, its manufacturing method, and a focal plane shutter blade using the same.

  Therefore, the present inventors have intensively studied to solve the above-described problems of the prior art, and as a result, Ni-based metal oxidation comprising a nano-order level Ni-based metal film layer and a crystal phase on both surfaces of the resin film by sputtering. In the light-shielding film in which a thin film of the material film layer is formed, the Ni-based metal film layer satisfies the light-shielding property, low reflectivity, sliding property, conductivity, heat resistance, high temperature resistance and high humidity resistance required as a shutter blade material. The shutter blade material operates at high speed by selecting the resin film base material so that the two characteristic values of the bending rigidity and tear strength of the shutter blade material on which the Ni-based metal oxide film layer is formed exceed a certain value. However, the inventors have found that a light-shielding film satisfying impact resistance and durability can be obtained at low cost, and have reached the present invention.

That is, according to 1st invention of this invention, it has Ni type metal film (B) which consists of a crystal phase with a film thickness of 40-250 nm on both surfaces of a resin film (A), and also is film | membrane on the outermost surface. A light-shielding film having a Ni-based metal oxide film (C) composed of a crystal phase having a thickness of 100 to 400 nm, the arithmetic average height Ra of the outermost surface being 0.1 to 2.1 μm, and having a wavelength of 380 to 780 nm The minimum optical density, which is an indicator of light shielding properties, exceeds 4, the maximum regular reflectance is less than 0.4%, the bending rigidity is 2.0 N · m ² / m or more, and the tear strength is 6.0 N / mm or more. And the light-shielding film characterized by a coefficient of dynamic friction being 0.2 or less is provided.

According to the second invention of the present invention, in the first invention, from the Ni-based metal film (B) immediately above both surfaces of the resin film (A) and the Ni-based metal oxide film (C) which is the outermost surface. A light-shielding film is provided.
According to a third aspect of the present invention, there is provided the light shielding film according to the first aspect, wherein the arithmetic average height Ra of the surface of the resin film (A) is 0.2 to 2.2 μm. Provided.
According to the fourth invention of the present invention, in the first invention, the bending rigidity of the resin film (A) is 1.5 N · m ² / m or more, and the tear strength is 5.0 N / mm or more. The light-shielding film characterized by this is provided.
According to a fifth aspect of the present invention, in the first aspect, the resin film (A) is any one selected from the group consisting of polyethylene terephthalate, polyethylene naphthalate, liquid crystal polymer, and polyetheretherketone. The light shielding film characterized by containing the resin component of this.

According to the sixth invention of the present invention, in the first invention, the Ni-based metal film (B) is mainly composed of nickel, and further includes titanium, tantalum, tungsten, vanadium, aluminum, molybdenum, cobalt, There is provided a light-shielding film comprising one or more additive elements (Em) selected from the group consisting of niobium, iron, copper, and zinc.
According to the seventh invention of the present invention, in the first or sixth invention, the content of the additive element (Em) in the Ni-based metal film (B) is 0. (Em / Ni) atomic ratio. The light-shielding film characterized by being 0.5-0.5 is provided.
According to the eighth invention of the present invention, in the first invention, the oxygen content of the Ni-based metal film (B) is 0.20 or less in terms of (O / Ni) atomic ratio. A light-shielding film is provided.
According to the ninth aspect of the present invention, in the first aspect, the Ni-based metal oxide film (C) is mainly composed of nickel, and further includes titanium, tantalum, tungsten, vanadium, aluminum, molybdenum, There is provided a light-shielding film comprising one or more additive elements (Eo) selected from the group consisting of cobalt, niobium, iron, copper, and zinc.
According to the tenth aspect of the present invention, in the first aspect, the content of the additive element (Eo) in the Ni-based metal oxide film (C) is 0.05 (Eo / Ni) atomic ratio. The light-shielding film characterized by being -0.5 is provided.
According to the eleventh aspect of the present invention, in the first aspect, the oxygen content of the Ni-based metal oxide film (C) is 0.65 to 0.85 in terms of (O / Ni) atomic ratio. The light-shielding film characterized by being is provided.

According to a twelfth aspect of the present invention, there is provided the light shielding film according to any one of the first to eleventh aspects, wherein the surface resistance value of the light shielding film is 500Ω / □ or less. .
According to the thirteenth aspect of the present invention, in any one of the first to eleventh aspects, the Ni-based metal film (B) and the Ni-based metal oxide film (C) are formed of a resin film substrate (A ), And a light-shielding film is provided.
Furthermore, according to the fourteenth aspect of the present invention, in the thirteenth aspect, the Ni-based metal film (B) and the Ni-based metal oxide film (C) have substantially the same film thickness and metal element composition. A light-shielding film is provided.

  According to the fifteenth aspect of the present invention, in any one of the first to fourteenth aspects, the resin film (A) having a surface roughness of arithmetic average height Ra of 0.2 to 2.2 μm is sputtered. The Ni-based metal film (B) is formed on the resin film (A) by sputtering at a film forming gas pressure of 0.2 to 1.0 Pa on the resin film (A). While oxygen gas is introduced onto the metal film (B) in an inert atmosphere, sputtering is performed with a film forming gas pressure of 0.2 to 1.0 Pa to mainly contain nickel, and titanium, tantalum, tungsten, and vanadium. Provided is a method for producing a light-shielding film, comprising forming a Ni-based metal oxide film (C) containing at least one selected from the group consisting of aluminum, molybdenum, cobalt, niobium, iron, copper and zinc The That.

According to the sixteenth aspect of the present invention, in the fifteenth aspect, the light shielding film in which the Ni-based metal film (B) and the Ni-based metal oxide film (C) are formed on one surface of the resin film (A). A film is further supplied to a sputtering apparatus, and a Ni-based metal film (B) and a Ni-based metal oxide film are sequentially formed on the other surface of the resin film (A) by sputtering. Is provided.
Furthermore, according to a seventeenth aspect of the present invention, in the fifteenth aspect, the resin film (A) is wound into a roll and set in a film transport section of a sputtering apparatus. A manufacturing method is provided.

On the other hand, according to the eighteenth aspect of the present invention, there is provided a focal plane shutter blade obtained by punching the light shielding film of any one of the first to fourteenth aspects.
According to a nineteenth aspect of the present invention, there is provided a focal plane shutter blade according to the eighteenth aspect, wherein the light shielding film has a total thickness of 75 to 125 μm.

It is sectional drawing which showed typically one Embodiment of the light shielding film of this invention. When forming a Ni-type metal oxide film, it is the graph which showed the change of O / Ni atomic number ratio which is the oxygen content in a film | membrane with respect to the oxygen flow rate ratio in sputtering gas. It is the graph which showed the film-forming speed | rate change in a film | membrane with respect to the oxygen flow rate ratio in sputtering gas, when forming a Ni type metal oxide film. It is the graph which showed the refractive index change with respect to a wavelength by Ni type metal oxide film (O / Ni atomic ratio is 0.88). It is the graph which showed the refractive index change with respect to a wavelength by Ni type metal oxide film (O / Ni atomic ratio is 0.80). It is the schematic of the winding-type sputtering apparatus which manufactures the light shielding film of this invention. It is the chart which showed the X-ray-diffraction pattern of the Ni-Ti oxide film which comprises the light shielding film (Example 1) of this invention. It is the chart which showed the X-ray-diffraction pattern of the Ni-Ti oxide film which comprises the light shielding film for a comparison (comparative example 11).

  Hereinafter, the light shielding film of the present invention, a method for producing the same, and a focal plane shutter blade using the same will be described with reference to FIGS.

1. Light-shielding film The light-shielding film of the present invention uses a resin film (A) as a base material and a Ni-based metal film (B) made of a crystal phase with a film thickness of 50 to 250 nm formed on both surfaces of the resin film (A) by a sputtering method. And a crystal phase with a film thickness of 100 nm to 400 nm formed on the Ni-based metal film (B) by a sputtering method and having an O / Ni atomic ratio of 0.65 to 0.85. And a Ni-based metal oxide film (C) having a minimum optical density of more than 4 at a wavelength of 380 to 780 nm, a maximum regular reflectance of 0.4% or less, and 2.0 N · m ² / m. It has the above bending rigidity and a tear strength of 6.0 N / mm or more.

  FIG. 1 is a schematic diagram showing a configuration of a light shielding film according to the present invention. The light shielding film of the present invention comprises a resin film 1 as a base material, a Ni-based metal film 2 formed on both surfaces thereof, and a Ni-based metal oxide film 3 formed thereon.

The surface roughness of the Ni-based metal oxide film 3 is 0.1 to 2.1 μm, more preferably 0.2 to 1.8 μm, and most preferably 0.3 to 1 in terms of arithmetic average height Ra. .5 μm. Arithmetic mean height is also called arithmetic mean roughness, and is extracted from the roughness curve by the reference length in the direction of the mean line, and the absolute value of the deviation from the mean line of the extracted part to the measurement curve is summed and averaged. It is the value.
If the surface roughness is less than 0.1 μm, the reflected light cannot be sufficiently scattered, so that the reflectivity cannot be kept low, and imaging defects due to leaked light reflected between the blades are not preferable. . On the other hand, when the thickness exceeds 2.1 μm, the unevenness of the surface becomes too large, the thickness of the Ni-based metal oxide film becomes non-uniform, and an extremely thin portion is generated. As a result, the film stress distribution becomes non-uniform and irregular deformation occurs, and there are places where it is difficult to suppress reflection at the interface of the underlying Ni-based metal light-shielding film. This is not preferable in that the regular reflectance cannot be lowered sufficiently.

Although the resin film 1 is not limited by thickness, it is desirable that it is the range of 75-125 micrometers, More preferably, it is 75-100 micrometers. If it is less than 75 μm, the flexural rigidity of the resin film is less than 1.5 N · m ² / m and the tear strength is less than 5.0 N / mm. Shutter obtained by punching the light-shielding film because the light-shielding film formed on the resin film cannot have a bending rigidity of 2.0 N · m ² / m and a tear strength of 6.0 N / mm or more. When the blade is slid at a high speed, the blade material may bend or deform, or a crack may occur in the end surface of the blade material. On the other hand, if it exceeds 125 μm, there may be no space for mounting a plurality of focal plane shutter blades in the focal plane shutter unit, which is becoming smaller.

  The Ni-based metal film must have a thickness of 40 to 250 nm. A film thickness of 40 nm or less is not preferable because light passing through the film occurs and the light shielding function is not sufficient. When the film thickness is increased, the light shielding property is improved. However, if it exceeds 250 nm, the production cost is increased due to an increase in material cost and film formation time, and the stress of the film is increased, which is not preferable. In consideration of sufficient light shielding properties (transmittance 0%), low film stress, and low manufacturing cost, the thickness of the Ni-based metal light shielding film is preferably 50 to 250 nm.

  The Ni-based metal oxide film must have a thickness of 100 to 400 nm. If the film thickness is 100 nm or less, it is difficult to suppress reflection at the interface of the underlying Ni-based metal film, and the maximum regular reflectance may not be sufficiently lowered, which is not preferable. When the film thickness exceeds 400 nm, when a Ni-based metal film and a Ni-based metal oxide film are formed on one side of the film, the deformation of the film due to the film stress becomes very large, and the film surface is cracked. This is not preferable. Furthermore, it is not preferable to form a film thickness exceeding 400 nm because the film forming time is very long and the manufacturing cost is high.

  The Ni-based metal film and the Ni-based metal oxide film need to be formed on both surfaces of the resin film, and the material and film thickness of the film on each surface are the same, and the structure is symmetrical about the film substrate. It is more preferable. Since the thin film formed on the film gives stress to the base material, it becomes a factor of deformation, and the deformation may be seen immediately after film formation. However, as described above, the Ni-based metal film and Ni-based metal oxide film formed on both sides of the film are made of the same material, and a symmetrical structure with the film as the center makes it possible to balance stress even under heating conditions. Therefore, it is easy to realize a light-shielding film having excellent flatness without warping or distortion.

The light-shielding film of the present invention has a minimum optical density of more than 4 at a wavelength of 380 to 780 nm, a maximum regular reflectance of 0.4% or less, a bending rigidity of 2.0 N · m ² / m or more, and 6.0 N. It has a tear strength of / mm or more. Unless the minimum optical density at a wavelength of 380 to 780 nm exceeds 4 and the maximum regular reflectance is 0.4% or less, the light shielding property is insufficient, which is not practical.
The light shielding film must have a bending rigidity of 2.0 N · m ² / m or more and a tear strength of 6.0 N / mm or more. If the bending stiffness is less than 2.0 N · m ² / m, it is not preferable because it may bend and deform due to impact at the time of sliding at high speed or at the time of stopping, resulting in damage. If the tear strength of the light-shielding film is 6.0 N / mm or more, even if a minute microcrack is generated on the end face portion of the blade material, the crack is not further increased. When the tear strength is less than 6.0 N / mm, the crack grows due to the impact at the time of sliding at high speed or at the stop starting from the microcrack generated at the end of the blade material, which is not preferable.

(A) Resin film The resin film which is the base material of the light-shielding film of the present invention has a light-shielding film having a bending rigidity of 2.0 N · m ² / m or more and a tear strength of 6.0 N when the light-shielding film is formed. / Mm or more, and one that can suppress deflection during sliding, occurrence of damage due to deformation, and growth of the damage is selected. Shutter blades used in digital single-lens reflex cameras are called focal plane shutter blades, and about 4 to 5 sheets are mounted on one shutter unit, and slide at a high shutter speed. Since each blade material slides and stops at high speed instantly, the load applied to the blade material is large, and the blade material collides with peripheral members in its movable area during sliding due to deformation of the blade material such as deflection and swell. Or, the blades rub against each other, and the blade material itself may be damaged or deformed, so that a good image may not be obtained.

Therefore, in the present invention, it is preferable to use a base material having a bending rigidity of 1.5 N · m ² / m or more and a tear strength of 5.0 N / mm or more. Those having such strength characteristics are manufactured by stretching in one direction or two directions when forming a resin material into a film.

The components of the resin film include polyacetal, polyamide, polycarbonate, modified polyphenylene ether, polybutylene terephthalate, polyarylate, polysulfone, polyethersulfone, polyphenylene, which are commercially available as engineering plastics or super engineering plastics. It is preferable to select or process a product satisfying the above properties from sulfide, polyethylene terephthalate, polyethylene naphthalate, liquid crystal polymer, polyetheretherketone, polyimide, polyamideimide, polyetherimide, or fluororesin.
Among these, products that satisfy the above characteristics among polyethylene terephthalate, polyethylene naphthalate, liquid crystal polymer, and polyetheretherketone, which have high bending rigidity and exhibit mechanical properties against deflection, deformation, and vibration during sliding of the blade material. It is preferable to select or process and use, and polyethylene terephthalate and polyethylene naphthalate are more preferable because they are cheaper and easily available.

  The thickness of the resin film that is the base material of the light-shielding film of the present invention is not particularly limited, but a resin film of 75 μm to 125 μm is preferable. If the thickness is less than 75 μm, the strength tends to be insufficient, and if it exceeds 125 μm, it may be too thick to be incorporated into the product as a blade material.

Moreover, the surface roughness of the surface is preferably 0.2 to 2.2 [mu] m as the arithmetic average height Ra, and further one having a fine uneven structure of 0.4 to 1.6 [mu] m on both sides is useful. is there. If there are irregularities on the surface of the resin film, the adhesion with the Ni-based metal film on the resin film will be good, and the surface of the Ni-based metal oxide film formed on the Ni-based metal film will be appropriately wavy. As a result, the maximum regular reflectance of light can be reduced and the effect of matting can be brought about, which is preferable as an optical member.
When the arithmetic average height Ra is smaller than 0.2 μm, the adhesion with the Ni-based metal film formed on the film surface becomes insufficient, and the Ni-based metal oxide film formed on the Ni-based metal film also has Sufficient low gloss and low reflectivity may not be obtained. Also, if the arithmetic average height Ra exceeds 2.2 μm, the unevenness of the film surface becomes too large, and the Ni-based metal film cannot be formed in the concave portion of the surface, resulting in surface defects such as pinholes. There is. In order to suppress the occurrence of such defects, it is necessary to sufficiently cover the film surface to obtain sufficient light shielding properties. In this case, the Ni-based metal film becomes thick, which is not preferable because of high cost.

The unevenness on the surface of the resin film is formed by surface-treating the film surface and the back surface. For example, although it is a simple method to obtain by carrying out the mat processing using a shot material, it is not limited to this. For example, in a film produced by a casting method, the concavo-convex structure is transferred by pouring a film resin dissolved in a solvent onto a support having a concavo-convex shape on the surface. A fine uneven structure may be formed on the surface by nanoimprinting. In addition, sand or the like is generally used as a shot material for mat processing, but is not limited thereto.
In the mat treatment, irregularities can be formed on the film surface while conveying the film. The unevenness of the optimal arithmetic average height Ra value depends on the film conveyance speed during the mat processing, the type of shot material, the particle size, and the discharge pressure of the shot material. The front and back surfaces are processed so that the height Ra value is 0.2 to 2.2 μm. The film after the mat treatment is washed to remove the shot material and then dried.

The base resin film may be composed of a transparent resin or a colored resin kneaded with a pigment or an inorganic filler. The resin is colored by kneading the inorganic filler, and the light-shielding property is in the direction of increasing. However, the mechanical properties of the resin film can be improved by selecting appropriate particles, their diameter, and addition amount. . Examples of inorganic fillers that improve mechanical properties include alumina, titanium oxide, silica, zinc oxide, and magnesium oxide. The average particle diameter of the inorganic filler is preferably 0.01 μm to 1 μm, for example. If it is less than 0.01 μm, it tends to agglomerate, and if it exceeds 1 μm, the arithmetic average height Ra value is difficult to match the above range.
When the inorganic filler is contained, the content varies depending on the average particle diameter, the type of inorganic filler, the type (component or thickness) of the resin, etc., but is 2 to 25 with respect to the resin (100 parts by weight of solid). Part by weight is preferable, 5 to 20 parts by weight is more preferable, and 8 to 15 parts by weight is particularly preferable. If the amount is less than 2 parts by weight, the effect of improving the characteristics is hardly seen, which is not preferable from the viewpoint of cost. The film cannot be stably produced, and the surface resistance value may increase.

(B) Ni-based metal film Generally, when a metal film is oxidized, the transparency increases. Therefore, the oxidation resistance of the metal film serving as a light shielding film is important.

  In the present invention, the Ni-based metal film is a Ni-based metal material excellent in oxidation resistance. Specifically, pure nickel may be used, but nickel, the main component, titanium, tantalum, tungsten, vanadium, aluminum, molybdenum Ni-based metal films containing one or more additive elements (Em) selected from the group consisting of cobalt, niobium, iron, copper, and zinc are preferable. In the Ni-based metal film to which these elements are added, nickel itself is less likely to be oxidized than pure nickel.

  When the Ni-based metal film is formed by sputtering, the Ni-based metal film has high density and good oxidation resistance, and has relatively good adhesion to the resin film. The additive element (Em) of the Ni-based metal film has an (Em / Ni) atomic number ratio of preferably 0.05 to 0.5, particularly preferably 0.05 to 0.2. If it is less than 0.05, the ferromagnetic characteristics of the nickel target cannot be extremely weakened, and film formation by DC magnetron sputtering may not be performed with a cathode on which a normal magnet having a weak magnetic force is disposed. Further, if it exceeds 0.5, a large amount of intermetallic compounds are formed, the brittleness of the sputtering target is increased, cracking due to thermal stress at the time of sputtering, etc., there is a possibility that sputtering cannot be performed, and the obtained Ni-based compound The metal film may also deteriorate in film quality such as increased brittleness.

Further, since the film formation speed in the sputtering film formation using the Ni-based target is faster than the sputtering film formation using other metal targets, the sputtering film formation is advantageous also in this aspect. For example, the deposition rate of a nickel film by direct current magnetron sputtering using a nickel target is about 1.5 to 2 times faster than the deposition rate of a titanium film under the same conditions using a titanium target.
The Ni-based metal film may contain carbon and nitrogen. In order to introduce carbon and nitrogen into the Ni-based metal film, an additive gas containing a carbon element or nitrogen element such as hydrocarbon gas or nitrogen gas is introduced into the sputtering gas when forming the Ni-based metal film, respectively. However, it is possible to introduce these elements by using carbon or nitrogen in the target without using the additive gas as described above. In particular, if the Ni-based metal film contains carbon and nitrogen, it is useful because the heat resistance can be further improved. Therefore, carbides such as nickel carbide, nickel nitride, nickel carbonitride, and nitrides and carbonitrides produced by the above method are also Ni-based metal film materials that exhibit sufficient light shielding properties and heat resistance, and resin films Therefore, it is included in the Ni-based metal film material of the light shielding film of the present invention.

Further, the Ni-based metal film of the present invention preferably contains no oxygen in order to maintain high adhesion to the resin film and high light shielding properties. Even if oxygen or the like remaining in the sputtering gas is incorporated into a part or the whole of the Ni-based metal film at the time of film formation, the metallic property, the high light-shielding property, and the high adhesion to the resin film are not impaired. Although there is no limitation, the content of oxygen in the Ni-based metal film is preferably 0.20 or less in terms of the O / Ni atomic ratio in order to maintain adhesion with the resin film.
When the oxygen content in the Ni-based metal film exceeds 0.20 in terms of the O / Ni atomic ratio, the transmittance of the film increases, the minimum optical density at a wavelength of 380 to 780 nm decreases, and light shielding properties are obtained. Therefore, the film thickness of the Ni-based metal film is increased. For this reason, the content of oxygen in the Ni-based metal film is preferably 0.20 or less and more preferably 0.15 or less in terms of the O / Ni atomic ratio from the viewpoint of light shielding properties.

(C) Ni-based metal oxide film In the present invention, the Ni-based metal oxide film is a Ni-based metal oxide film containing nickel as a main component. The Ni-based metal oxide film mainly composed of nickel has excellent heat resistance and corrosion resistance in a high heat environment, and the underlying Ni-based metal light-shielding film (B) mainly composed of nickel and the metal component. In the same manner, the adhesion with the underlying Ni-based metal film is easily improved.

This Ni-based metal oxide film, unlike the Ni-based metal film, must contain a large amount of oxygen. As the amount of oxygen contained, the O / Ni atomic ratio is 0.65 to 0.85. Preferably there is. This is because it is necessary to obtain sufficient values in the optical characteristics such as the maximum regular reflectance and the minimum optical density, and the corrosion of the Ni-based metal film portion does not proceed in a high-temperature and high-humidity atmosphere and the durability is not deteriorated. The O / Ni atomic ratio is more preferably 0.7 to 0.85, and further preferably 0.75 to 0.85.
The Ni-based metal oxide film may be a nickel oxide film whose metal component is composed only of nickel, but is mainly composed of nickel, and further, titanium, tantalum, tungsten, vanadium, aluminum, molybdenum, cobalt, niobium, A crystalline Ni-based metal oxide film containing at least one additional element (Eo) selected from the group consisting of iron, copper and zinc is preferable.
Further, the additive element (Eo) of the Ni-based metal oxide film is contained in the range of 0.05 to 0.50, particularly 0.05 to 0.20 as the (Eo / Ni) atomic ratio. Is preferred. If it is less than 0.05, the ferromagnetic characteristics of the nickel target cannot be extremely weakened, and film formation by DC magnetron sputtering may not be performed with a cathode on which a normal magnet having a weak magnetic force is disposed. Further, if it exceeds 0.5, a large amount of intermetallic compounds are formed, the brittleness of the sputtering target is increased, cracking due to thermal stress at the time of sputtering, etc., there is a possibility that sputtering cannot be performed, and the obtained Ni-based compound The metal oxide film may also deteriorate in film quality, such as increasing brittleness.

In the Ni-based metal oxide film of the present invention, a reactive gas such as oxygen gas is introduced as a sputtering gas into an inert gas such as argon gas, and the Ni-based sputtering target is sputtered in the same manner as the Ni-based metal film. It is obtained with.
In reactive sputtering, there are three modes with different film formation rates and film qualities, and generally there are three states called metal mode, transition mode, and oxide mode. As a relationship between the reactive gas flow rate ratio and the sputtering voltage or film formation rate, the oxygen flow rate indicating the ratio of oxygen gas flow rate / (oxygen gas flow rate + inert gas flow rate) in the sputtering gas during Ni-based metal oxide film formation. The relationship between the sputtering voltage and the deposition rate of the Ni-based metal oxide film shows the hysteresis that the behavior when the oxygen flow ratio is increased does not match the behavior when the oxygen flow ratio is decreased. Is a feature.

Briefly describing the states of these three modes, the metal mode is a state in which only an insufficient amount of oxygen gas is present in the chamber so that the entire target surface used reacts with oxygen to form a metal oxide film. is there. For this reason, the target surface is gradually covered with the metal oxide film by the oxygen gas, and the sputtering voltage gradually increases. However, there are many metal parts not covered with the metal oxide film, and the metal particles This is because the sputtering is preferentially performed. Therefore, the deposition rate becomes very high with respect to the oxygen flow rate ratio in the sputtering gas (hereinafter simply referred to as the oxygen flow rate ratio), and a metallic film can be obtained.
On the other hand, in the oxide mode, a sufficient amount of oxygen gas is present in the chamber so that the entire target surface to be used reacts with oxygen to become a metal oxide film, and the target surface is covered with the metal oxide film. State. As a result, the sputtering voltage decreases and the film formation rate becomes very slow.
Further, the transition mode is a state in which the transition from the metal mode to the oxide mode is abrupt, and the range of the oxygen flow rate ratio that becomes the transition mode is very narrow, so that it is difficult to control the sputtering in the transition mode. The obtained film quality is an intermediate characteristic between the metal state and the metal oxide state, but due to a slight difference in the oxygen flow rate ratio, the film quality tends to be closer to the metal state or closer to the metal oxide state. End up.

  As described above, in reactive sputtering, film formation in the transition mode is difficult to control. Therefore, in the case of stable industrial use, film formation in the oxide mode is performed to form a desired metal oxide. It has become common to obtain membranes. However, since it is advantageous in terms of film quality modification and film formation speed, attempts have been made to industrially use sputtering in the transition mode.

Similarly, the Ni-based target used in the present invention takes three modes with respect to the oxygen flow rate ratio.
FIG. 2 shows the amounts of Ni and O calculated from X-ray photoelectron spectroscopic analysis (also referred to as XPS) with respect to the oxygen flow rate ratio representing the introduction ratio of the reactive gas during the formation of the Ni-based metal oxide film. An example of the relationship of the O / Ni atomic ratio was shown. FIG. 3 shows an example of increasing the oxygen flow rate ratio in the relationship between the deposition rate of the Ni-based metal oxide film and the oxygen flow rate ratio during film formation.

As can be seen from FIG. 2, the O / Ni atomic number ratio indicating the oxygen content in the Ni-based metal oxide film increases as the oxygen flow rate ratio increases. As shown in FIG. 3, the reactive sputtering mode when the oxygen flow rate ratio is increased is changed from the reactive sputtering state to the metal mode, transition mode, and oxide mode as the O / Ni atomic ratio increases. And change.
The region where the O / Ni atomic ratio is less than 0.65 is a region where the oxygen flow rate ratio is less than 50% from FIG. 2 and, as can be seen from FIG. Most of the film is not covered with a Ni-based metal oxide film, and the film forming speed is high. However, the color of the Ni-based metal oxide film exhibits a metallic color, resulting in a film having a strong metallic luster. In such a composition range, an oxide film having an appropriate oxygen concentration is formed only partially, and the distribution is not uniform, resulting in variations in composition. For this reason, there are many Ni-based metal film portions having a low oxygen concentration, and it is not possible to obtain sufficient values in optical characteristics such as maximum regular reflectance and minimum optical density. In heat resistance / high temperature and high humidity resistance evaluation, Ni As the corrosion of the metallic metal film proceeds, the durability may deteriorate and the characteristics may not be stable.

  On the other hand, the region exceeding 0.85 is obtained on the high oxygen flow rate ratio side in the transition mode or oxide mode, and the target surface is completely covered with the Ni-based metal oxide film. slow. As the O / Ni atomic ratio increases, the transmittance of the film increases, the refractive index of the film decreases, and the maximum regular reflectance on the film surface decreases as compared to the Ni-based metal oxide film obtained in the metal mode. FIG. 4 shows the refractive index in the visible light region (wavelength 380 to 780 nm) when the O / Ni atomic ratio is 0.88. It can be seen that the change in the refractive index with respect to the wavelength of visible light is large. Since the reflectance varies depending on the refractive index of the object, when a Ni-based metal oxide film having an O / Ni atomic ratio exceeding 0.85 is laminated, the difference in reflectance at each wavelength is large. Therefore, even if the film thickness adjustment or composition ratio adjustment of the Ni-based metal oxide film is performed, a wavelength with high reflectivity exists and blackening becomes difficult. Furthermore, since the crystallinity of the Ni-based metal oxide film disappears and becomes an amorphous film, the orientation of crystal grains becomes random, so the durability such as heat resistance, high temperature and high humidity resistance is poor. Furthermore, the bending rigidity and tear strength of the light-shielding film tend to be worse than in the case of the crystal film.

  As described above, the oxygen content of the Ni-based metal oxide film of the present invention is preferably such that the O / Ni atomic ratio is 0.65 to 0.85. Such a film is obtained in a region on the high oxygen flow ratio side in the metal mode before the transition mode. The film obtained in this region has a Ni and O amount uniform in the film and has crystallinity for film formation in the metal mode, compared to the above-described film formation on the low oxygen flow rate ratio side. Therefore, unlike the Ni-based metal oxide film obtained on the low oxygen flow ratio side of the metal mode, the structure is uniform, so that it is excellent in durability under a high temperature environment or a high temperature and high humidity environment. FIG. 5 shows the refractive index in the visible light region (wavelength 380 to 780 nm) when the O / Ni atomic ratio is 0.75. It can be seen that the change in the refractive index with respect to the wavelength in the visible light region is small. Since the change in refractive index is small, the difference in reflectance at each wavelength is also small. Further, since the Ni-based metal oxide film in this composition range is colored, it is more appropriate to adjust the film thickness and composition ratio. It becomes possible to make it black.

The material of the Ni-based metal oxide film may not be the same as that of the Ni-based metal film, but is preferably a Ni-based metal oxide film having the same component as the Ni-based metal film. As a result, both a Ni-based metal film and a Ni-based metal oxide film can be formed using a single sputtering target, and can be manufactured with a sputtering apparatus having a single cathode. Can be reduced. The reflectance of visible region can be reduced by setting the film thickness of the Ni-based metal oxide film containing nickel as a main component to 100 to 400 nm.
If the film thickness is less than 100 nm, it is difficult to suppress reflection at the interface of the underlying Ni-based metal film, and the maximum regular reflectance may not be sufficiently reduced. When the thickness exceeds 400 nm, when a Ni-based metal film and a Ni-based metal oxide film are formed on one side of the film, the deformation of the film due to film stress becomes very large, and the film surface may crack, which is not preferable. . Furthermore, since it takes a very long film formation time to form a film thickness exceeding 400 nm, it is not preferable in terms of manufacturing cost.

When a plastic film is used as the base material, the plastic film is easily insulated due to its insulating properties. When operated as shutter blades or diaphragm blades, static electricity is generated by contact between the blades, and the blades are attracted by electrostatic adsorption. Since they may adsorb each other, it is important to have excellent conductivity in order to release the generated static electricity.
The film material used for the light-shielding film of the present invention is a Ni-based metal and a Ni-based metal oxide, both of which are Ni-based metal materials having excellent conductivity. As the Ni-based metal film and the Ni-based metal oxide film, the metal component may be pure nickel. However, in the present invention, the Ni-based metal film has nickel as a main component and is further selected from the group consisting of titanium, tantalum, tungsten, vanadium, aluminum, molybdenum, cobalt, niobium, iron, copper, or zinc. The Ni-based metal oxide film containing the above elements is mainly selected from the group consisting of nickel, titanium, tantalum, tungsten, vanadium, aluminum, molybdenum, cobalt, niobium, iron, copper, or zinc. More preferably, it contains one or more elements. By adding the above elements, the added elements have a dopant-like action in a semiconductor, and electrical resistance can be reduced.
Further, as described above, since the Ni-based metal oxide film is formed in the metal mode in the present invention, the surface resistance of the film is extremely lower than the film obtained in the general oxide mode. In the light-shielding film whose outermost surface is formed of an insulating film such as silicon oxide or alumina as a protective film, the surface resistance value is about 10 ⁴ Ω / □, but the light-shielding film of the present invention has a surface resistance value of 500 Ω / square. □ or less, preferably 100 Ω / □ or less, and more preferably 50 Ω / □ or less.

In the light-shielding film of the present invention described above, the minimum optical density at a wavelength of 380 to 780 nm, which is a light-shielding index, exceeds 4, and the maximum regular reflectance is 0.4% or less.
The optical density is a numerical value obtained by converting the transmittance (T) of each wavelength measured by a spectrophotometer according to the following equation (1). In order to obtain complete light-shielding properties, the minimum optical density at a wavelength of 380 to 780 nm needs to be at least 4 or more, and the oxygen content in the Ni-based metal film is 0.20 in terms of the O / Ni atomic ratio. It is obtained by the following.

[Equation 1]
Optical density = Log (1 / T) (1)

The regular reflectance of light refers to the reflectance of light reflected from the surface at an angle equal to the incident angle of incident light according to the law of reflection, and the maximum positive reflectance is required to obtain sufficient low reflectivity. It is necessary that the regular reflectance does not exceed 0.4%. This low reflectivity can be obtained by setting the thickness of the Ni-based metal oxide film to 100 nm or more, or setting the surface roughness of the Ni-based metal oxide film to 0.1 or more in terms of arithmetic average height Ra. .
As long as the characteristics of the present invention are not impaired, the light-shielding film of the present invention has other thin films (for example, fluorine-containing organic films, etc.) having lubricity and low friction on the surface of the Ni-based metal oxide film. A carbon film, diamond-like carbon film, etc.) may be applied thinly.

2. Manufacturing method of light-shielding film The light-shielding film of the present invention supplies a resin film (A) having a surface roughness of 0.2 to 2.2 μm with an arithmetic average height Ra to a sputtering apparatus, and a film forming gas pressure is 0.2. Sputtering in an inert gas atmosphere of ˜1.0 Pa to form a Ni-based metal film (B) on the resin film (A), and then forming a film gas while introducing oxygen gas into the inert gas atmosphere Sputtering is performed at a pressure of 0.2 to 1.0 Pa to form a Ni-based metal oxide film (C) on the Ni-based metal film (B).

The resin film (A) is generally selected from engineered plastics or super engineering plastics, such as commercially available polyethylene terephthalate, polyethylene naphthalate, liquid crystal polymer, polyetheretherketone, or the like. Those having a bending rigidity of 1.5 N · m ² / m or more and a tear strength of 5.0 N / mm or more are preferred.

In the present invention, a Ni-based metal film is first formed on the surface of the resin film by a sputtering method, and then a colored Ni-based metal oxide film having an antireflection effect is formed on the Ni-based metal film by sputtering. Form. In the present invention, since the Ni-based metal film and the Ni-based metal oxide film are formed by the sputtering method, the film has better denseness than the conventional ink coating method or vacuum deposition method, and the base (substrate or Good adhesion to the film).
For light-shielding films formed by conventional ink coating or vacuum deposition methods, the light-shielding film can be used in a high-temperature and high-humidity environment with a temperature of 85 ° C and humidity of 90% RH, or after processing into a blade material, it slides at high speed. In such a case, the film is peeled off or the color changes due to the oxidation of the film. However, the Ni-based metal film and the light-shielding film made of the Ni-based metal oxide film formed according to the present invention do not cause such a problem.

  The light-shielding film in the present invention is produced by forming a Ni-based metal film and a Ni-based metal oxide film on a resin film substrate by sputtering as described above. The sputtering method is an effective thin film forming method when a film of a material having a low vapor pressure is formed on a substrate or when precise film thickness control is required. In general, under an inert gas pressure of about 10 Pa or less, the base material is an anode, the sputtering target that is the raw material of the film is the cathode, and glow gas is generated during this time to generate an inert gas plasma, In this method, an inert gas cation in plasma is collided with a sputtering target of a cathode, particles of the sputtering target component are blown off, and the particles are deposited on a substrate to form a film.

Sputtering methods are classified according to the method of generating an inert gas plasma. A method using high frequency plasma is a high frequency sputtering method, and a method using direct current plasma is a direct current sputtering method. In the magnetron sputtering method, a magnet is disposed on the back side of a sputtering target, and inert gas plasma is concentrated directly on the sputtering target to increase the collision efficiency of inert gas ions even at a low gas pressure.
In order to form the Ni-based metal film and the Ni-based metal oxide film, for example, a winding type sputtering apparatus as shown in FIG. 6 can be used. First, the roll-shaped resin film 1 is set on the unwinding roll 4 and the inside of the vacuum chamber 6 is exhausted by a vacuum pump 5 such as a turbo molecular pump. Thereafter, the resin film 1 is unwound from the unwinding roll 4, passes through the surface of the can roll 7, and is wound up by the winding roll 8. A single magnetron cathode 9 is installed on the opposite side of the surface of the can roll 7, and a target 10 which is a raw material for the film is attached to this cathode. Simultaneously with transporting the resin film 1, a Ni-based metal film or a Ni-based metal oxide film is formed on the resin film 1 which is discharged and transported between the can roll 7 and the cathode. In addition, the film conveyance part comprised by the unwinding roll 4, the winding roll 8, etc. is isolated from the can roll 7, the single magnetron cathode 9, etc. by the partition 11.

As the inert gas used in the sputtering method used in the production of the light-shielding film of the present invention, it is preferable to mainly use argon gas or helium gas. Hereinafter, a case where argon gas is mainly used as the inert gas will be described as an example, but the inert gas is not limited to argon gas.
In the light-shielding film of the present invention, the Ni-based metal film is formed on the resin film substrate by a direct current magnetron sputtering method using a pure nickel or Ni-based alloy sputtering target in an argon gas atmosphere, for example.
Since the pure nickel material is a ferromagnetic material, when the Ni-based metal film layer is formed by the direct current magnetron sputtering method, the magnet disposed on the back surface of the sputtering target for acting on the plasma between the sputtering target and the substrate is used. The magnetic field leaked to the surface becomes weak when the magnetic force is shielded by the nickel target material, and it becomes difficult to concentrate the plasma and efficiently form a film. In order to avoid this, it is desirable to use a cathode in which the magnetic force of a magnet arranged on the back side of the sputtering target is increased and to increase the magnetic field passing through the nickel sputtering target to perform sputtering and form a film.
However, even when such a method is adopted, another problem as described below occurs during production. That is, when the thickness of the sputtering target decreases with continuous use of the nickel target, the leakage magnetic field in the plasma space becomes stronger in the portion where the thickness of the sputtering target is reduced. When the leakage magnetic field in the plasma space becomes strong, the discharge characteristics change and the film formation rate changes. That is, when the same nickel target is continuously used for a long time during production, there arises a problem that the deposition rate of the nickel film changes as the nickel target is consumed.

Therefore, in such a case, one or more kinds of additive elements (Em) selected from titanium, tantalum, tungsten, vanadium, aluminum, molybdenum, cobalt, niobium, iron, copper, and zinc containing nickel as a main component are included. By using a Ni-based metal material as a target, ferromagnetism is weakened, the above problem can be avoided, and a Ni-based metal film having the above composition can be formed. In the present invention, it is desirable to use a Ni-based metal material containing the additive element (Em) content in a ratio of the number of atoms with Ni (Em / Ni) in the range of 0.05 to 0.5 as the target. .
The reason for defining the additive element (Em) content as described above is that a normal magnet having a weak magnetic force can be obtained by making the ferromagnetic properties extremely weak by adding 0.05 or more in terms of the number of atoms with nickel. This is because film formation by direct current magnetron sputtering can be performed even with a cathode in which is arranged. In addition, since the shielding capability of the magnetic field by the sputtering target is low, the change in the leakage magnetic field in the plasma space depending on the consumption of the sputtering target is small, and stable film formation is possible at a constant film formation rate. The reason why the additive element (Em) content is 0.5 or less in terms of the number of atoms with nickel is that when the additive element (Em) exceeds 0.5, a large amount of intermetallic compound is added. Since the brittleness of the sputtering target is increased, the sputtering target may break due to thermal stress during sputtering, and sputtering may not be possible, and the film quality of the metal alloy film obtained by sputtering may deteriorate. It is.

The sputtering gas pressure at the time of forming the Ni-based metal film (B) varies depending on the type of the apparatus and the like, and thus cannot be generally specified, but is 1.0 Pa or less, for example, 0.2 to 1.0 Pa. It is preferable to make it. As a result, even if a small amount of the shot material used in the mat treatment remains on the resin film, the thermal expansion difference and blade material of the shot material, Ni-based metal film, Ni-based metal oxide film in a high-temperature and high-humidity environment The film is also difficult to peel off due to stress during sliding. When the sputtering gas pressure at the time of film formation is less than 0.2 Pa, the gas pressure is low, so that the argon gas plasma in the sputtering method becomes unstable, and the film quality of the formed film is deteriorated. In addition, when the sputtering gas pressure at the time of film formation exceeds 1.0 Pa, the Ni-based metal film becomes coarse and the film is not highly dense, so the adhesion with the resin film is weakened and the film is peeled off. End up.
When the Ni-based metal film of the present invention does not contain oxygen, high adhesion to the resin film and high light-shielding properties can be maintained, so oxygen gas is not introduced into the sputtering gas. Even if oxygen or the like remaining in the sputtering gas is incorporated into a part or the whole of the Ni-based metal film at the time of film formation, the metallic property, the high light-shielding property, and the high adhesion to the resin film are not impaired. Although there is no limitation, the sputtering gas is controlled so that the oxygen content in the Ni-based metal film is 0.20 or less in terms of the O / Ni atomic ratio in order to maintain adhesion to the resin film. It is preferable.

Next, the Ni-based metal oxide film (C) is formed, but even in this film-forming process, the same target is used without changing the sputtering target used for sputtering the Ni-based metal film (B). Can be used.
In order to form the Ni-based metal oxide film (C) of the present invention, it is necessary to introduce oxygen gas into the sputtering gas. The sputtering gas pressure at the time of film formation varies depending on the type of apparatus and the like, and thus cannot be specified unconditionally. It is preferable to make it. When the sputtering gas pressure at the time of film formation is less than 0.2 Pa, the gas plasma becomes unstable because the gas pressure is low, and the film quality of the formed film deteriorates. Moreover, when the sputtering gas pressure at the time of film formation exceeds 1.0 Pa, the Ni-based metal oxide film (C) grains become coarse, and the adhesiveness with the resin film becomes weak because the film quality is not high. Therefore, it is not preferable. In addition, when the sputtering gas pressure exceeds 1.0 Pa, it is not preferable because the formed metal oxide film tends to be amorphous even if the oxygen content is small.
It is preferable to introduce oxygen gas into the sputtering gas so that the oxygen content in the Ni-based metal oxide film (C) is 0.65 to 0.85 in terms of the O / Ni atomic ratio. In the region where the O / Ni atomic ratio is less than 0.65, there is a portion with insufficient oxidation and a metallic luster, and in addition to being unable to obtain a sufficient value in optical properties, heat resistance and high temperature resistance In high-humidity evaluation, corrosion of the metal film portion proceeds and durability is deteriorated. In the region where the O / Ni atomic ratio exceeds 0.85, the film formation is performed in the oxide mode, so that not only the film formation rate is slow, but the permeability of the film increases as the O / Ni atomic ratio increases. In addition to the decrease in the refractive index of the film, the Ni-based metal oxide film (C) becomes amorphous and the heat resistance, high temperature resistance and high humidity resistance decrease, which is not preferable.

By using the same target as the sputtering target used in the sputtering of the Ni-based metal film (B) in the Ni-based metal oxide film (C) film forming step, the Ni-based metal film is formed on one surface of the base film. And a light-shielding film having a Ni-based metal oxide film formed thereon. In order to obtain a light-shielding film in which a Ni-based metal film and a Ni-based metal oxide film are formed on both sides, the light-shielding film in which a Ni-based metal film and a Ni-based metal oxide film are formed on one side is further provided with the above sputtering apparatus. The Ni-based metal film and the Ni-based metal oxide film are sequentially formed on the back surface of the resin film by sputtering according to the same method.
By using this method, it is not necessary to replace the target set in the apparatus, and continuous sputtering is possible. Therefore, the manufacturing cost is reduced, and a symmetrical film structure centered on a heat-resistant resin film is provided. Since it can be formed, a light shielding film that does not cause deformation of the light shielding film due to film stress after film formation can be obtained in high yield.

  The film winding type sputtering apparatus is exemplified to form the Ni-based metal film and the Ni-based metal oxide film, and the method for continuously forming the film has been described in detail. However, the present invention is not limited to this. It is also possible to adopt a batch-type film formation method that is performed without moving the base film during film formation. In this case, operations such as switching of the atmospheric gas and loading / stopping of the film are added and complicated. When employing the batch-type film formation method, the base film may be fixed in the apparatus in a state of being cut into a predetermined size, even if it is not a roll-shaped film.

3. Use of light shielding film The light shielding film of the present invention can be used as a material for a focal plane shutter blade of a digital single lens reflex camera.

In order to use the light-shielding film of the present invention as a focal plane shutter blade of a digital single-lens reflex camera, a punching process that does not cause surface and end face cracks may be performed by a known method.
Since the focal plane shutter blade obtained in the present invention possesses sufficient bending rigidity and tear strength, it can be used as a shutter blade for a high-speed digital single-lens reflex camera. Therefore, the weight can be reduced as compared with the conventional high-speed shutter blades, and the drive member for driving the shutter blades can be downsized and the power consumption can be reduced.

  Next, the present invention will be specifically described using examples and comparative examples, but the present invention is not limited only to the examples. In addition, evaluation of the resin base film of material and the obtained light shielding film was performed with the following method.

(Tear strength of resin base film and light shielding film)
The tear strength is a universal material testing machine (model 5566 manufactured by INSTRON), trouser method (according to ASTM D1938), with a test piece size of 75 x 25 mm, a 50 mm slit in the test piece, and a test speed of 250 mm / min. Measured with The tear strength was a value obtained by dividing the average load (N) by the thickness (mm) of the test piece.
When the tear strength of the light-shielding film is 6.0 N / mm or more, the following impact resistance test shows good strength at which cracks do not easily grow from the notch at the end.

(Bending rigidity of resin base film and light shielding film)
The bending rigidity is obtained by cutting a resin base film or a light shielding film into a 200 mm square, and using an automated pure bending tester (KES-FB2-AUTO-A manufactured by Kato Tech Co., Ltd.) to give a certain curvature to the light shielding film. It was measured as a bending moment per 1 cm width. When the light blocking film has a flexural rigidity of 2.0 N · m ² / m or more, it exhibits good rigidity with no deformation in the following impact resistance test.

(Minimum optical density and maximum regular reflectance of light-shielding film)
The maximum regular reflectance and the minimum optical density at a wavelength of 380 to 780 nm were measured with a spectrophotometer (V-570 manufactured by JASCO Corporation). The maximum regular reflectance was measured at an incident angle of 5 °. When the minimum optical density exceeds 4.0, when the maximum regular reflectance is less than 0.4% and there is almost no change in the heat resistance / high temperature resistance test, the light shielding property is good.

(Surface roughness of resin base film and light shielding film)
For the surface roughness, the arithmetic average height Ra of the sample was measured with a surface roughness meter (manufactured by Tokyo Seimitsu Co., Ltd., Surfcom 570A).

(Composition analysis of Ni-based metal film and Ni-based metal oxide film)
The amount of nickel and oxygen in the film was measured after cleaning the outermost surface of the film by sputter etching with an X-ray photoelectron spectrometer (XPS, ESCALAB220i-XL manufactured by VG Scientific).

(Crystalline analysis of Ni-based metal oxide film)
A single Ni-based metal oxide film formed on a glass substrate was analyzed for crystallinity using a two-dimensional X-ray diffractometer (D8 DISCOVER μ-HR manufactured by Bruker AXS).

(Conductivity)
The surface resistance value of the obtained light shielding film was measured based on JIS K6911 with a resistivity meter (Loresta EPMCP-T360, manufactured by Mitsubishi Chemical Analic). When the surface resistance value is 500Ω / □ or less, the generated static electricity is well removed.

(Dynamic friction coefficient)
The dynamic friction coefficient was measured according to JIS K7125 using a universal material testing machine (5566 model manufactured by INSTRON). When the coefficient of dynamic friction is 0.2 or less, good slidability is exhibited.

(Impact resistance of punched shading film)
A 10 mmφ hole was punched on the surface of a strip-shaped light-shielding film (50 mm × 30 mm) to obtain a test piece. Insert a pin into the hole, and use an ultrasonic fatigue tester (manufactured by Shimadzu Corporation) to vibrate the sample up and down at a frequency of 10 kHz while applying a 5N load, and end the end face on the 10 mmφ hole side. And the number of cycles until a crack occurred in the end face of the hole was counted.
The time when cracks occurred at 2 million times or more was judged as good.

(The heat resistance of the light-shielding film)
Regarding the heat resistance of the light-shielding film, heat treatment is performed at 85 ° C. for 1 hour in an atmospheric oven (manufactured by Advantech Co., Ltd.), and the maximum regular reflectance of the film, the value of the minimum optical density, whether there is a change, and the film adhesion Examined. Further, the film adhesion was evaluated by visually checking whether there was no film peeling, (◯) when there was no film peeling, or (×) when the film was peeled off.

(High temperature and high humidity resistance of shading film)
About the high temperature resistance and high humidity resistance of the light-shielding film, the process of 85 degreeC x 90% RH * 24hr was performed with the small environmental tester (SH-241 by ESPEC CORP.). Evaluation was performed in the same manner as the heat resistance.

Example 1
A Ni-based metal film and a Ni-based metal oxide film were formed on the resin film 1 using the winding type sputtering apparatus shown in FIG. First, a target 10 serving as a film raw material was attached to the cathode of an apparatus in which a magnetron cathode 9 was installed on the opposite side of the surface of the can roll 7. A film transport unit including the unwinding roll 4 and the winding roll 8 is separated from the can roll 7 and the magnetron cathode 9 by a partition wall 11.
As the roll-shaped resin film 1, a polyethylene terephthalate film having a bending rigidity of 4.3 N · m ² / m, a tear strength of 9.1 N / mm and a thickness of 100 μm was used. First, sand blasting was performed on the surface of the film at a predetermined discharge time, discharge pressure, and conveyance speed to form fine irregularities with an arithmetic average height of Ra 0.5 μm on both surfaces.
Subsequently, this polyethylene terephthalate film is set on the unwinding roll 4 and is heated and dried at a temperature of 60 ° C. or higher before sputtering while running the film using a can roll 7 or a heater installed in the sputtering apparatus. It wound up with the winding roll 8.
Next, the inside of the vacuum chamber 6 is evacuated by a vacuum pump 5 such as a turbo molecular pump, and then discharged between the can roll 7 and the cathode 9 to form a film while closely transporting the resin film 1 to the surface of the can roll 7. It was. First, a Ni-based alloy (hereinafter abbreviated as Ni-Ti) target containing nickel as a main component and containing 9 atomic% (also referred to as at%) of titanium is placed on the cathode 9, and Ni—Ti is formed from the cathode 9 by DC magnetron sputtering. A metal film (Em / Ni atomic ratio = 0.1) was formed. The Ni—Ti metal film was formed using pure argon gas (purity 99.999%) as the sputtering gas. The target input power density was 14 kW / cm ² , the gas pressure was 0.3 Pa, and the film thickness was 90 nm, which was controlled by the film transport speed during film formation. After the heat drying, the resin film 1 wound up on the take-up roll 8 was taken out from the take-up roll 8 as it was, passed through the surface of the can roll 7 on the way, and taken up with the take-up roll 4.
Then, in the state which wound the roll-shaped resin film in which the Ni-Ti metal film was formed with the unwinding roll 4, a film was continuously conveyed from the unwinding roll 4 with the Ni-Ti target installed in the cathode. From this cathode, a Ni—Ti metal oxide film (Eo / Ni atomic ratio = 0.1) was formed on the Ni—Ti film by direct current sputtering. The reactive gas at the time of forming the Ni—Ti metal oxide film is oxygen gas (purity 99.999%), mixed with argon gas in the gas pipe, introduced into the cathode, and oxygen gas with respect to the argon gas. The oxygen flow rate ratio representing the ratio was 53%. This oxygen flow rate ratio corresponds to the metal mode region before the transition region in FIG. 2 showing the relationship between the oxygen flow rate ratio of the Ni-based metal film and the deposition rate. The Ni—Ti metal oxide film was formed at a target input power density of 6.7 W / cm ² and a gas pressure of 0.3 Pa. The film thickness was controlled by the film conveyance speed during film formation, and was 200 nm. At the time of forming the Ni—Ti metal oxide film, the resin film 1 carried out from the unwinding roll 4 was taken up by the take-up roll 8 through the surface of the can roll 7 on the way. Thereby, the film in which the Ni—Ti film having a thickness of 90 nm and the Ni—Ti metal oxide film having a thickness of 200 nm were formed on one surface of the film base material was obtained.
Next, the inside of the vacuum chamber 6 is opened to the atmosphere, and the polyethylene terephthalate film having the Ni—Ti metal film and the Ni—Ti metal oxide film wound on the take-up roll 8 is taken out on one side, and the back side is the same. In order to form the film, the orientation was set on the unwinding roll 4. Thereafter, a Ni—Ti metal film and a Ni—Ti metal oxide film were formed on the back surface of the polyethylene terephthalate film in the same manner, and a light shielding film having a symmetrical structure with the polyethylene terephthalate film as the center was produced.
Further, the Ni and Ti contents of each film were examined by XPS analysis for a light-shielding film in which a single layer film of a Ni—Ti metal film and a Ni—Ti metal oxide film was formed on a polyethylene terephthalate film. As a result, when the oxygen content of the Ni—Ti film was expressed by the O / Ni atomic ratio, it was 0.12, and the Ni—Ti metal oxide film was 0.75. The X-ray diffraction analysis result of the Ni—Ti metal oxide film is shown in FIG. 7, and the Ni—Ti metal oxide film was a crystal film.
Next, the produced light shielding film was evaluated by the said method. As a result, the minimum optical density at a wavelength of 380 to 780 nm exceeded 4, and the maximum regular reflectance was as good as 0.3%. The dynamic friction coefficient was 0.2, which was good. Further, the surface resistance was 70Ω / □, and the arithmetic average height of the surface was 0.4 μm.
Even in the heat resistance test and the high temperature and high humidity resistance test, the minimum optical density and the maximum specular reflectance did not change, and no warpage occurred, which was good. The film adhesion was also good with no film peeling.
The obtained light-shielding film has a flexural rigidity of 5.2 N · m ² / m and a tear strength of 9.6 N / mm, which is higher than that of polyethylene terephthalate alone by forming a film and exhibits good mechanical properties. It was. In addition, as a result of producing a punched sample and conducting a durability test, the end face of the punched hole was not cracked or deformed up to 6 million cycles due to impact with the pin, and showed excellent durability.
The construction of the produced light shielding film is summarized in Table 1.
Therefore, the obtained light-shielding film is good in all of the minimum optical density, maximum specular reflectance, heat resistance / high temperature and humidity resistance, friction coefficient, conductivity, and impact resistance, and the focal plane of a single-lens reflex digital camera. It is extremely useful industrially as a shutter blade application.
Table 1 shows the characteristics of the Ni-based metal film and the Ni-based metal oxide film, and Table 2 shows the initial characteristics of the produced light-shielding film and the changes in characteristics in heat resistance, high temperature resistance and high humidity.

(Example 2)
A light-shielding film was produced under exactly the same conditions as in Example 1 except that the thickness of the polyethylene terephthalate film was changed to 75 μm. By reducing the thickness of the substrate, the resin film had a flexural rigidity of 1.6 N · m ² / m and a tear strength of 5.4 N / mm, which were lower than those in Example 1, and lower in flexural rigidity and tear strength.
The light-shielding film was evaluated by the same method and conditions as in Example 1. As a result, the minimum optical density, maximum regular reflectance, surface resistance, dynamic friction coefficient, arithmetic average height Ra, bending rigidity, tear strength, and impact resistance characteristics met the standards as in Example 1. In the heat resistance and high temperature and high humidity resistance tests, the minimum optical density and the maximum specular reflectance do not change, the film adhesion does not peel off, and the same heat resistance and high temperature and high humidity resistance as in Example 1 are obtained. I found it. The construction of the produced light shielding film is summarized in Table 1. Table 2 shows the initial characteristics of the produced light-shielding film and the changes in characteristics in heat resistance, high temperature resistance and high humidity.
Therefore, the obtained light-shielding film is good in all of the minimum optical density, maximum specular reflectance, heat resistance / high temperature and humidity resistance, friction coefficient, conductivity, and impact resistance, and the focal plane of a single-lens reflex digital camera. It is extremely useful industrially as a shutter blade application.

Example 3
A light-shielding film was produced under exactly the same conditions as in Example 1 except that the thickness of the polyethylene terephthalate film was changed to 125 μm. By increasing the thickness of the resin film substrate, the flexural rigidity and tear strength were higher than those of Example 1 with a flexural rigidity of 8.3 N · m ² / m and a tear strength of 11.3 N / mm.
The light-shielding film was evaluated by the same method and conditions as in Example 1. As a result, the minimum optical density, maximum specular reflectance, surface resistance, dynamic friction coefficient, arithmetic average height Ra, bending rigidity, tear strength, and impact resistance characteristics met the standards as in Example 1. In the heat resistance and high temperature and high humidity resistance tests, the minimum optical density and the maximum specular reflectance do not change, the film adhesion does not peel off, and the same heat resistance and high temperature and high humidity resistance as in Example 1 are obtained. I found it. The construction of the produced light shielding film is summarized in Table 1. Table 2 shows the initial characteristics of the produced light-shielding film and the changes in characteristics in heat resistance, high temperature resistance and high humidity.
Therefore, the obtained light-shielding film is good in all of the minimum optical density, maximum specular reflectance, heat resistance / high temperature and humidity resistance, friction coefficient, conductivity, and impact resistance, and the focal plane of a single-lens reflex digital camera. It is extremely useful industrially as a shutter blade application.

Example 4
A light-shielding film was produced under exactly the same conditions as in Example 1 except that the type of the resin film substrate was changed to a polyethylene naphthalate film. The polyethylene naphthalate film having a thickness of 75 μm had a flexural rigidity of 2.2 N · m ² / m and a tear strength of 6.2 N / mm.
The light-shielding film was evaluated by the same method and conditions as in Example 1. As a result, the minimum optical density, maximum specular reflectance, surface resistance, dynamic friction coefficient, arithmetic average height Ra, bending rigidity, tear strength, and impact resistance characteristics met the standards as in Example 1. By forming a film on the film, the bending rigidity and tear strength were slightly increased. In the heat resistance and high temperature and high humidity resistance tests, the minimum optical density does not change, the change in the maximum specular reflectance is small, and the film adhesion does not peel off. It was found to have high temperature and high humidity. The construction of the produced light shielding film is summarized in Table 1. Table 2 shows the initial characteristics of the produced light-shielding film and the changes in characteristics in heat resistance, high temperature resistance and high humidity.
Therefore, the obtained light-shielding film is good in all of the minimum optical density, maximum specular reflectance, heat resistance / high temperature and humidity resistance, friction coefficient, conductivity, and impact resistance, and the focal plane of a single-lens reflex digital camera. It is extremely useful industrially as a shutter blade application.

(Example 5)
A light-shielding film was produced under exactly the same conditions as in Example 4 except that the thickness of the resin film substrate was changed to 100 μm. The polyethylene naphthalate film having a thickness of 100 μm had a flexural rigidity of 4.5 N · m ² / m and a tear strength of 8.3 N / mm.
The light-shielding film was evaluated by the same method and conditions as in Example 4. As a result, the minimum optical density, maximum regular reflectance, surface resistance, dynamic friction coefficient, arithmetic average height Ra, bending rigidity, tear strength, and impact resistance characteristics met the standards as in Example 1. By forming a film on the film, the bending rigidity and tear strength were slightly increased. Also in the heat resistance and high temperature and high humidity resistance tests, the minimum optical density does not change, the change in the maximum specular reflectance is small, and the film adhesion does not peel off. It was found to have high temperature and high humidity. The construction of the produced light shielding film is summarized in Table 1. Table 2 shows the initial characteristics of the produced light-shielding film and the changes in characteristics in heat resistance, high temperature resistance and high humidity.
Therefore, the obtained light-shielding film is good in all of the minimum optical density, maximum specular reflectance, heat resistance / high temperature and humidity resistance, friction coefficient, conductivity, and impact resistance, and the focal plane of a single-lens reflex digital camera. It is extremely useful industrially as a shutter blade application.

(Example 6)
A light-shielding film was produced under exactly the same conditions as in Example 4 except that the thickness of the resin film substrate was changed to 125 μm. The polyethylene naphthalate film having a thickness of 125 μm had a flexural rigidity of 8.7 N · m ² / m and a tear strength of 10.4 N / mm.
The light-shielding film was evaluated by the same method and conditions as in Example 4. As a result, the minimum optical density, the maximum regular reflectance, the surface resistance, the dynamic friction coefficient, the arithmetic average height Ra, the bending rigidity, the tear strength, and the impact resistance characteristics met the standards as in Example 4. By forming a film on the film, the bending rigidity and tear strength were slightly increased. In the heat resistance and high temperature and high humidity resistance tests, the minimum optical density and the maximum specular reflectance do not change, the film adhesion does not peel off, and it has the same heat resistance, high temperature and high humidity resistance as in Example 4. I found out. The construction of the produced light shielding film is summarized in Table 1. Table 2 shows the initial characteristics of the produced light-shielding film and the changes in characteristics in heat resistance, high temperature resistance and high humidity.
Therefore, the obtained light-shielding film is good in all of the minimum optical density, maximum specular reflectance, heat resistance / high temperature and humidity resistance, friction coefficient, conductivity, and impact resistance, and the focal plane of a single-lens reflex digital camera. It is extremely useful industrially as a shutter blade application.

(Example 7)
A light-shielding film was produced under the same conditions as in Example 1 except that the resin film was changed to polyether ether ketone having a thickness of 100 μm.
The polyether ether ketone film having a thickness of 100 μm had a flexural rigidity of 3.6 N · m ² / m and a tear strength of 7.6 N / mm.
The light-shielding film was evaluated by the same method and conditions as in Example 1. As a result, the minimum optical density, maximum regular reflectance, surface resistance, dynamic friction coefficient, arithmetic average height Ra, bending rigidity, tear strength, and impact resistance characteristics met the standards as in Example 1. By forming a film on the film, the bending rigidity and tear strength were slightly increased. Also in the heat resistance and high temperature and high humidity resistance tests, the minimum optical density did not change and the maximum specular reflectance was slightly lower in the high temperature and high humidity resistance tests, and the film adhesion was not peeled off. It was found to have heat resistance, high temperature resistance and high humidity resistance as in Example 1. The construction of the produced light shielding film is summarized in Table 1. Table 2 shows the initial characteristics of the produced light-shielding film and the changes in characteristics in heat resistance, high temperature resistance and high humidity.
Therefore, the obtained light-shielding film is good in all of the minimum optical density, maximum specular reflectance, heat resistance / high temperature and humidity resistance, friction coefficient, conductivity, and impact resistance, and the focal plane of a single-lens reflex digital camera. It is extremely useful industrially as a shutter blade application.

(Example 8)
A light-shielding film was produced under the same conditions as in Example 1 except that the resin film was changed to a liquid crystal polymer film having a thickness of 100 μm.
The liquid crystal polymer film having a thickness of 100 μm had a flexural rigidity of 3.4 N · m ² / m and a tear strength of 7.3 N / mm.
The light-shielding film was evaluated by the same method and conditions as in Example 1. As a result, the minimum optical density, maximum regular reflectance, surface resistance, dynamic friction coefficient, arithmetic average height Ra, bending rigidity, tear strength, and impact resistance characteristics met the standards as in Example 1. By forming a film on the film, the bending rigidity and tear strength were slightly increased. In the heat resistance and high temperature and high humidity resistance tests, the minimum optical density and the maximum specular reflectance do not change, and the adhesion of the film does not peel off. I found it. The construction of the produced light shielding film is summarized in Table 1. Table 2 shows the initial characteristics of the produced light-shielding film and the changes in characteristics in heat resistance, high temperature resistance and high humidity.
Therefore, the obtained light-shielding film is good in all of the minimum optical density, maximum specular reflectance, heat resistance / high temperature and humidity resistance, friction coefficient, conductivity, and impact resistance, and the focal plane of a single-lens reflex digital camera. It is extremely useful industrially as a shutter blade application.

(Comparative Example 1)
A light-shielding film was produced under exactly the same conditions as in Example 1 except that the thickness of the polyethylene terephthalate film was changed to 50 μm. By reducing the thickness of the resin film substrate, the bending rigidity and tear strength were lower than those of Example 1 with a flexural rigidity of 0.5 N · m ² / m and a tear strength of 4.5 N / mm.
The light-shielding film was evaluated by the same method and conditions as in Example 1. As a result, the minimum optical density, the maximum regular reflectance, the surface resistance, the dynamic friction coefficient, the arithmetic average height Ra, the heat resistance, the high temperature and high humidity resistance, and the film adhesion were the same as in Example 1 and were good. However, with respect to impact resistance, the film was deformed after 700,000 cycles, and cracks were generated in the hole end face portion after 1 million cycles. This is presumably because the impact resistance was inferior to that of Example 1 because of low bending rigidity and tear strength.
The structure of the produced light shielding film was put together in Table 1,2.
Therefore, the obtained light-shielding film was good in minimum optical density, maximum regular reflectance, heat resistance / high temperature and humidity resistance, friction coefficient, and conductivity, but poor in impact resistance. It cannot be used as a focal plane shutter blade. However, it is industrially very useful for the shutter blade material of a compact digital camera in which the shutter speed is lower than that of a single-lens reflex digital camera and the number of mounted digital cameras is small.

(Comparative Example 2)
A light-shielding film was produced under exactly the same conditions as in Example 1 except that the thickness of the polyethylene naphthalate film was changed to 50 μm. By reducing the thickness of the resin film substrate, the flexural rigidity was 0.6 N · m ² / m, the tear strength was 4.1 N / mm, and the flexural strength and tear strength were lower than in Example 1.
The light-shielding film was evaluated by the same method and conditions as in Example 1. As a result, the minimum optical density, the maximum regular reflectance, the surface resistance, the dynamic friction coefficient, the arithmetic average height Ra, the heat resistance, the high temperature and high humidity resistance, and the film adhesion were the same as in Example 1 and were good. However, with respect to impact resistance, deformation occurred in the film in 1 million cycles, and cracks occurred in the hole end face portion in 12,000,000 cycles. This is presumably because the impact resistance was inferior to that of Example 1 because of low bending rigidity and tear strength.
The structure of the produced light shielding film was put together in Table 1,2. Therefore, the obtained light-shielding film was good in minimum optical density, maximum regular reflectance, heat resistance / high temperature and humidity resistance, friction coefficient, and conductivity, but poor in impact resistance. It cannot be used as a focal plane shutter blade. However, it is industrially very useful for the shutter blade material of a compact digital camera in which the shutter speed is lower than that of a single-lens reflex digital camera and the number of mounted digital cameras is small.

(Comparative Examples 3 and 4)
The resin film was changed to a black PET film having a thickness of 75 μm (Comparative Example 3) and 100 μm (Comparative Example 4). This black PET film is mainly used as a shutter blade material for a digital camera or the like, and has a light shielding layer of several μm formed on the film surface layer portion. In this case, the Ni metal light-shielding film and the Ni-based metal oxide film were not formed on both surfaces of the black PET film, and the black PET film alone was evaluated by the same method and conditions as in Example 1.
The bending rigidity of the 75 μm thick black PET film was 1.4 N · m ² / m, and the tear strength was 1.0 N / mm. Further, the bending rigidity with a thickness of 100 μm was 3.1 N · m ² / m, and the tear strength was 4.8 N / mm.
In Comparative Examples 3 and 4, the minimum optical density, the maximum regular reflectance, the dynamic friction coefficient, the heat resistance, and the high temperature and high humidity resistance were the same as in Example 1 and were good. However, with respect to impact resistance, many cracks were generated from the end face at 500,000 cycles in Comparative Example 3 and 1 million cycles in Comparative Example 4. In all cases, the impact resistance was inferior to that of Example 1.
Further, the surface resistance value was 10,000 Ω / □, which was much higher than that in Example 1. Since the surface resistance of the black PET film is affected by the amount and dispersibility of the black pigment in the film resin, it is difficult to reduce the resistance. The characteristics of the black PET film are summarized in Tables 1 and 2.
Therefore, the black PET film with thickness of 75μm and 100μm has good minimum optical density, maximum specular reflectance, heat resistance, high temperature and humidity resistance, and good friction coefficient, but it has poor impact resistance and conductivity. As a focal plane shutter blade for a camera, it cannot be used on a mounting part that requires the most impact resistance.

Example 9
The production method, conditions, and evaluation of the light-shielding film were performed in the same manner as in Example 1 except that the film conveyance speed during the mat treatment was changed and the arithmetic average height Ra of the polyethylene terephthalate film was changed to 0.2 μm.
As a result, the minimum optical density, the maximum regular reflectance, the surface resistance, the dynamic friction coefficient, the heat resistance, the high temperature and high humidity resistance, the film adhesion, and the impact resistance met the standards as in Example 1.
The construction of the produced light shielding film is summarized in Table 1. Table 2 shows the initial characteristics of the produced light-shielding film and the changes in characteristics in heat resistance, high temperature resistance and high humidity.
Therefore, the obtained light-shielding film has good minimum optical density, maximum specular reflectance, heat resistance, high temperature and humidity resistance, coefficient of friction, electrical conductivity, and impact resistance. It is extremely useful industrially as a use.

(Example 10)
The production method, conditions, and evaluation of the light-shielding film were performed in the same manner as in Example 1 except that the film conveyance speed during the mat treatment was changed and the arithmetic average height Ra of the polyethylene terephthalate film was changed to 2.2 μm.
As a result, the minimum optical density, the maximum regular reflectance, the surface resistance, the dynamic friction coefficient, the heat resistance, the high temperature and high humidity resistance, the film adhesion, and the impact resistance met the standards as in Example 1. In particular, the maximum regular reflectance was such that the arithmetic average height Ra of the resin film substrate was increased, so that light scattering increased on the surface, leading to a decrease in the maximum regular reflectance.
The construction of the produced light shielding film is summarized in Table 1. Table 2 shows the initial characteristics of the produced light-shielding film and the changes in characteristics in heat resistance, high temperature resistance and high humidity.
Therefore, the obtained light-shielding film has good minimum optical density, maximum specular reflectance, heat resistance, high temperature and humidity resistance, coefficient of friction, electrical conductivity, and impact resistance. It is extremely useful industrially as a use.

(Comparative Example 5)
The production method, conditions, and evaluation of the light-shielding film were performed in the same manner as in Example 1 except that the film conveyance speed during the mat treatment was changed and the arithmetic average height Ra of the polyethylene terephthalate film was changed to 0.1 μm.
As a result, the minimum optical density, surface resistance, coefficient of dynamic friction, heat resistance, high temperature and humidity resistance, film adhesion, and impact resistance met the standards as in Example 1. However, since the arithmetic average height Ra of the resin film substrate was small and the surface flatness was increased, light scattering on the film surface was suppressed, and the maximum regular reflectance exceeded 0.4%.
Tables 1 and 2 summarize the structures and characteristics of the produced light-shielding films.
Therefore, the obtained light-shielding film has good minimum optical density, heat resistance, high temperature and humidity resistance, friction coefficient, conductivity, and impact resistance, but has a high maximum regular reflectance, and therefore requires low reflectance. Although it cannot be used as a shutter blade material of a digital camera, it can be used for parts that do not care much about reflection in the lens and shutter unit.

(Comparative Example 6)
The production method, conditions, and evaluation of the light-shielding film were performed in the same manner as in Example 1 except that the film conveyance speed during the mat treatment was changed and the arithmetic average height Ra of the polyethylene terephthalate film was changed to 2.3 μm.
As a result, many pinholes were confirmed on the surface of the light shielding film. Since the arithmetic average height is large, it is considered that the film surface was disturbed by the convex portion where the film surface was large and the film was not sufficiently formed by sputtering in the concave portion. Since there are many appearance defects of the light-shielding film, Comparative Example 6 was not evaluated. Tables 1 and 2 summarize the structures and characteristics of the produced light-shielding films.
The obtained light-shielding film has many pinholes and cannot be used as a shutter blade material for a digital camera because complete light-shielding properties cannot be obtained.

(Example 11)
The same method and conditions as in Example 1 except that the oxygen flow rate ratio during the formation of the Ni—Ti metal film was 20% and the composition of the Ni—Ti metal film (O / Ni atomic%) was changed to 0.2. It was made with.
As a result of evaluating the produced light-shielding film under the same method and conditions as in Example 1, as shown in Table 1, the minimum optical density, maximum specular reflectance, surface resistance, dynamic friction coefficient, arithmetic average height Ra, heat resistance, The high-temperature and high-humidity resistance, film adhesion, and impact resistance met the standards as in Example 1. The construction of the produced light shielding film is summarized in Table 1. Table 2 shows the initial characteristics of the produced light-shielding film and the changes in characteristics in heat resistance, high temperature resistance and high humidity.
Therefore, the obtained light-shielding film has good minimum optical density, maximum specular reflectance, heat resistance, high temperature and humidity resistance, friction coefficient, electrical conductivity, and impact resistance. As can be used.

(Comparative Example 7)
Exactly the same conditions as in Example 1 except that the oxygen flow rate ratio during the formation of the Ni—Ti metal film was adjusted to 25% and the O / Ni atomic ratio in the Ni—Ti metal film was changed to 0.3. A light shielding film was prepared.
The light-shielding film was evaluated by the same method and conditions as in Example 1. As a result, the maximum regular reflectance, surface resistance, arithmetic average height Ra, and impact resistance met the standards as in Example 1. However, the minimum optical density was 3.7, and complete light-shielding properties were not obtained. For this reason, dynamic friction coefficient, heat resistance, and high temperature and high humidity resistance were not evaluated. Tables 1 and 2 summarize the structures and characteristics of the produced light-shielding films.
Therefore, the obtained light-shielding film has a minimum optical density of less than 4.0, and therefore cannot be used as shutter blades or diaphragm blades for camera phones, smartphones, compact digital cameras, as well as digital single-lens reflex cameras.

(Example 12)
A light-shielding film was produced under exactly the same conditions as in Example 1 except that the thickness of the Ni—Ti metal film was changed to 50 nm.
The light-shielding film was evaluated by the same method and conditions as in Example 1. As a result, the minimum optical density, maximum regular reflectance, surface resistance, dynamic friction coefficient, arithmetic average height Ra, and impact resistance characteristics met the standards as in Example 1. Furthermore, in the heat resistance / high temperature high humidity test, the characteristics and film adhesion were good. The construction of the produced light shielding film is summarized in Table 1. Table 2 shows the initial characteristics of the produced light-shielding film and the changes in characteristics in heat resistance, high temperature resistance and high humidity.
Therefore, the obtained light-shielding film has good optical density, maximum specular reflectance, heat resistance, high temperature and humidity resistance, friction coefficient, conductivity, and impact resistance, and can be used as a focal plane shutter blade for single-lens reflex digital cameras. Can be used.

(Example 13)
A light shielding film was produced under exactly the same conditions as in Example 1 except that the thickness of the Ni—Ti metal film was changed to 250 nm.
The light-shielding film was evaluated by the same method and conditions as in Example 1. As a result, the minimum optical density, maximum regular reflectance, surface resistance, dynamic friction coefficient, arithmetic average height Ra, and impact resistance characteristics met the standards as in Example 1. Further, in the heat resistance / high temperature and high humidity resistance test, the characteristics and film adhesion were good. The construction of the produced light shielding film is summarized in Table 1. Table 2 shows the initial characteristics of the produced light-shielding film and the changes in characteristics in heat resistance, high temperature resistance and high humidity.
Therefore, the obtained light-shielding film has good minimum optical density, maximum specular reflectance, heat resistance, high temperature and humidity resistance, friction coefficient, electrical conductivity, and impact resistance. As can be used.

(Comparative Example 8)
A light shielding film was produced under exactly the same conditions as in Example 1 except that the thickness of the Ni—Ti metal film was changed to 40 nm.
The light-shielding film was evaluated by the same method and conditions as in Example 1. As a result, the maximum specular reflectance, surface resistance, coefficient of dynamic friction, arithmetic average height Ra, and impact resistance characteristics met the same standards as in Example 1, but the minimum optical density was 3.8, satisfying complete light-shielding properties. 4.0 was not obtained. For this reason, dynamic friction coefficient, heat resistance, and high temperature and high humidity resistance were not evaluated. Tables 1 and 2 summarize the structures and characteristics of the produced light-shielding films.
Therefore, since the obtained light-shielding film does not have complete light-shielding properties, it cannot be used for devices such as digital cameras as well as digital single-lens reflex cameras.

(Comparative Example 9)
A light-shielding film was produced under exactly the same conditions as in Example 1 except that the thickness of the Ni—Ti metal film was changed to 270 nm.
The light-shielding film was evaluated by the same method and conditions as in Example 1. As a result, the minimum optical density, maximum regular reflectance, surface resistance, dynamic friction coefficient, arithmetic average height Ra, and impact resistance characteristics met the standards as in Example 1. However, the film thickness of the Ni—Ti metal film became too thick, and remarkable film deformation was observed when the film was formed on one side of the film, and the deformation could not be improved even after film formation on both sides of the film. Tables 1 and 2 summarize the structures and characteristics of the produced light-shielding films.
Therefore, the obtained light-shielding film is excellent in optical properties, surface resistance, impact resistance, friction coefficient, heat resistance, high temperature and high humidity resistance, but the film is deformed by film stress because of its thick film thickness, Since it cannot be mounted on a camera module or the like, it is not preferable.

(Example 14)
Example 1 except that the oxygen flow rate ratio during the formation of the Ni—Ti metal oxide film was adjusted to 49% and the O / Ni atomic ratio of the Ni—Ti metal oxide film was changed to 0.65. A light-shielding film was produced under exactly the same conditions.
The light-shielding film was evaluated by the same method and conditions as in Example 1. As a result, the minimum optical density, maximum regular reflectance, surface resistance, dynamic friction coefficient, arithmetic average height Ra, and impact resistance characteristics met the standards as in Example 1. In the heat resistance and high temperature and high humidity resistance tests, the minimum optical density and the maximum specular reflectance do not change, the film adhesion does not peel off, and the same heat resistance and high temperature and high humidity resistance as in Example 1 are obtained. I found it. The construction of the produced light shielding film is summarized in Table 1. Table 2 shows the initial characteristics of the produced light-shielding film and the changes in characteristics in heat resistance, high temperature resistance and high humidity.
Therefore, the obtained light-shielding film has good minimum optical density, maximum specular reflectance, heat resistance, high temperature and humidity resistance, friction coefficient, electrical conductivity, and impact resistance. As can be used.

(Example 15)
Example except that the oxygen flow rate ratio during the formation of the Ni—Ti metal oxide film was adjusted to 53.5% and the O / Ni atomic ratio of the Ni—Ti metal oxide film was changed to 0.85. A light-shielding film was produced under exactly the same conditions as in 1.
The light-shielding film was evaluated by the same method and conditions as in Example 1. As a result, the characteristics of the minimum optical density, the maximum regular reflectance, the surface resistance, the dynamic friction coefficient, and the arithmetic average height Ra met the standards as in Example 1. In the heat resistance and high temperature and high humidity resistance tests, the minimum optical density and the maximum specular reflectance do not change, the film adhesion does not peel off, and the same heat resistance and high temperature and high humidity resistance as in Example 1 are obtained. I found it. The construction of the produced light shielding film is summarized in Table 1. Table 2 shows the initial characteristics of the produced light-shielding film and the changes in characteristics in heat resistance, high temperature resistance and high humidity.
Therefore, the obtained light-shielding film has good minimum optical density, maximum specular reflectance, heat resistance, high temperature and humidity resistance, friction coefficient, electrical conductivity, and impact resistance. As can be used.

(Comparative Example 10)
Example 1 except that the oxygen flow rate ratio during the formation of the Ni—Ti metal oxide film was adjusted to 48% and the O / Ni atomic ratio of the Ni—Ti metal oxide film was changed to 0.62. A light-shielding film was produced under exactly the same conditions.
The light-shielding film was evaluated by the same method and conditions as in Example 1. As a result, the minimum optical density, maximum regular reflectance, surface resistance, dynamic friction coefficient, arithmetic average height Ra, and impact resistance characteristics met the standards as in Example 1. However, in the heat resistance test and the high temperature and high humidity resistance test, the maximum specular reflectance changed greatly, and it was found that there was no heat resistance and high temperature and high humidity resistance. Tables 1 and 2 summarize the structures and characteristics of the produced light-shielding films.
Therefore, since the obtained light shielding film does not have heat resistance and high temperature and high humidity resistance, it cannot be used for shutter blade materials related to digital cameras.

(Comparative Example 11)
Example 1 except that the oxygen flow rate ratio during the formation of the Ni—Ti metal oxide film was adjusted to 55% and the O / Ni atomic ratio of the Ni—Ti metal oxide film was changed to 0.88. A light-shielding film was produced under exactly the same conditions. The oxygen flow rate ratio of 55% corresponds to the oxide mode region in FIG. 2 showing the relationship of the deposition rate of the Ni-based metal film to the oxygen flow rate ratio.
The light-shielding film was evaluated by the same method and conditions as in Example 1. As a result, the characteristics of the minimum optical density, the dynamic friction coefficient, and the arithmetic average height Ra met the standards as in Example 1.
However, the maximum specular reflectance exceeds 0.4%, which is higher than Example 1, and the maximum specular reflectance changes in the heat resistance and high temperature and high humidity resistance tests, and there is no heat resistance and high temperature and humidity resistance. I understood. Moreover, although the Ni—Ti metal film and the Ni—Ti metal oxide film were formed in the bending rigidity and tear strength of the light shielding film, the mechanical characteristics were not sufficiently improved.
FIG. 8 shows an X-ray diffraction pattern of the Ni—Ti metal oxide film. The Ni—Ti metal oxide film was amorphous. Therefore, it was found that when the amorphous film was formed, the mechanical properties of the light shielding film were not improved. Tables 1 and 2 summarize the structures and characteristics of the produced light-shielding films.
Therefore, since the obtained light-shielding film has poor light-shielding properties, heat resistance, and high-temperature and high-humidity resistance, it cannot be used for a focal plane shutter blade of a digital single-lens reflex camera having a high shutter speed.

(Example 16)
A light-shielding film was produced under exactly the same conditions as in Example 1 except that the thickness of the Ni—Ti metal oxide film was changed to 100 nm.
The light-shielding film was evaluated by the same method and conditions as in Example 1. As a result, the minimum optical density, maximum regular reflectance, surface resistance, dynamic friction coefficient, arithmetic average height Ra, and impact resistance characteristics met the standards as in Example 1. Further, in the heat resistance / high temperature and high humidity resistance test, the characteristics and film adhesion were good. The construction of the produced light shielding film is summarized in Table 1. Table 2 shows the initial characteristics of the produced light-shielding film and the changes in characteristics in heat resistance, high temperature resistance and high humidity.
Therefore, the obtained light shielding film is useful as a focal plane shutter blade material for a digital single lens reflex camera.

(Example 17)
A light-shielding film was produced under exactly the same conditions as in Example 1 except that the thickness of the Ni—Ti metal oxide film was changed to 400 nm.
The light-shielding film was evaluated by the same method and conditions as in Example 1. As a result, the minimum optical density, maximum regular reflectance, surface resistance, dynamic friction coefficient, arithmetic average height Ra, and impact resistance characteristics met the standards as in Example 1. Further, in the heat resistance / high temperature and high humidity resistance test, the characteristics and film adhesion were good. The construction of the produced light shielding film is summarized in Table 1. Table 2 shows the initial characteristics of the produced light-shielding film and the changes in characteristics in heat resistance, high temperature resistance and high humidity.
Therefore, the obtained light shielding film is useful as a focal plane shutter blade material for a digital single lens reflex camera.

(Comparative Example 12)
A light-shielding film was produced under exactly the same conditions as in Example 1 except that the thickness of the Ni—Ti metal oxide film was changed to 80 nm.
The light-shielding film was evaluated by the same method and conditions as in Example 1. As a result, the minimum optical density, surface resistance, dynamic friction coefficient, arithmetic average height Ra, and impact resistance characteristics met the same standards as in Example 1, but the maximum regular reflectance exceeded 0.4%. It was higher than 1. In addition, the characteristics and film adhesion in the heat resistance / high temperature and high humidity resistance test were good. Tables 1 and 2 summarize the structures and characteristics of the produced light-shielding films.
Therefore, since the obtained light-shielding film has a high maximum regular reflectance in the visible light region, the light reflected on the surface of the light-shielding film becomes stray light and enters the image sensor in the camera module, which may deteriorate the image quality. There is sex. Therefore, it cannot be used as a focal plane shutter blade material of a digital single lens reflex camera requiring low reflection.

(Comparative Example 13)
A light-shielding film was produced under exactly the same conditions as in Example 1 except that the thickness of the Ni—Ti metal oxide film was changed to 420 nm.
The light-shielding film was evaluated by the same method and conditions as in Example 1. As a result, the characteristics of the minimum optical density, the maximum regular reflectance, the surface resistance, and the arithmetic average height Ra met the standards as in Example 1. However, the film thickness of the Ni—Ti metal oxide film became too thick, and remarkable film deformation was observed when the film was formed on one side of the film, and the deformation could not be improved even after film formation on both sides of the film. Due to the large deformation of the light-shielding film, the impact resistance test, dynamic friction coefficient, heat resistance, high temperature resistance and high humidity resistance were not evaluated. Tables 1 and 2 summarize the structures and characteristics of the produced light-shielding films.
Therefore, the obtained light-shielding film is not preferable because the film is thick and deforms due to film stress and cannot be mounted on a camera module or the like.

(Examples 18, 19, and 20)
As a target for a Ni-based metal film and a Ni-based metal oxide film, a Ni-based alloy containing nickel as a main component and 6 at% of tungsten (Em / Ni atomic ratio and Eo / Ni atomic ratio is 0.06, Example 18) ), Ni-based alloy containing nickel as a main component and copper at 33 at% (Em / Ni atomic ratio and Eo / Ni atomic ratio is 0.5, Example 19), nickel as a main component and molybdenum at 22.5 at% A light-shielding film was produced in the same manner as in Example 1 except that the Ni-based alloy was changed (Em / Ni atomic ratio and Eo / Ni atomic ratio were 0.29, Example 20). Since the oxygen flow rate ratio at the time of film formation satisfying the optical characteristics equivalent to the Ni—Ti metal oxide film obtained in Example 1 was different from that in Example 1, the oxygen flow rate ratio was adjusted respectively.
Tables 1 and 2 summarize the compositions of various Ni-based metal films and Ni-based metal oxide films and the characteristics of the produced light-shielding films. The properties of the light-shielding film met the same standards as in Example 1, had no change in properties in the heat resistance / high temperature and humidity resistance test, and had good properties such as impact resistance.
Therefore, the obtained light shielding film is useful as a focal plane shutter blade material for a digital single lens reflex camera.

  The light-shielding film of the present invention has a high light-shielding property and low reflectivity in the visible light region, good slidability and impact resistance, and durability in a high-temperature environment and a high-temperature and high-humidity environment. It is useful as an inexpensive focal plane shutter blade material for digital SLR cameras.

Claims (19)

On both surfaces of the resin film (A), there is a Ni-based metal film (B) having a crystal phase with a film thickness of 40 to 250 nm, and a Ni-based metal oxide having a crystal phase with a film thickness of 100 to 400 nm on the outermost surface. A light-shielding film having a material film (C),
The arithmetic average height Ra of the outermost surface is 0.1 to 2.1 μm, the minimum optical density, which is an index of light shielding properties at a wavelength of 380 to 780 nm, exceeds 4, and the maximum regular reflectance is less than 0.4%. The light-shielding film has a bending rigidity of 2.0 N · m ² / m or more, a tear strength of 6.0 N / mm or more, and a dynamic friction coefficient of 0.2 or less.   2. The light-shielding film according to claim 1, comprising a Ni-based metal film (B) immediately above both surfaces of the resin film (A) and a Ni-based metal oxide film (C) which is the outermost surface.   2. The light-shielding film according to claim 1, wherein the arithmetic average height Ra of the surface of the resin film (A) is 0.2 to 2.2 μm. The light-shielding film according to claim 1, wherein the resin film (A) has a flexural rigidity of 1.5 N · m ² / m or more and a tear strength of 5.0 N / mm or more.   The light-shielding film according to claim 1, wherein the resin film (A) contains any resin component selected from the group consisting of polyethylene terephthalate, polyethylene naphthalate, liquid crystal polymer, and polyether ether ketone. .   The Ni-based metal film (B) is mainly composed of nickel, and further includes at least one selected from the group consisting of titanium, tantalum, tungsten, vanadium, aluminum, molybdenum, cobalt, niobium, iron, copper, and zinc. The light shielding film according to claim 1, further comprising an additive element (Em).   The additive element (Em) content of the Ni-based metal film (B) is 0.05 to 0.5 in terms of (Em / Ni) atomic number ratio, The light-shielding film according to claim 1 or 6 .   2. The light-shielding film according to claim 1, wherein the oxygen content of the Ni-based metal film (B) is 0.20 or less in terms of an (O / Ni) atomic ratio.   The Ni-based metal oxide film (C) has nickel as a main component and is further selected from the group consisting of titanium, tantalum, tungsten, vanadium, aluminum, molybdenum, cobalt, niobium, iron, copper, and zinc. The light-shielding film according to claim 1, comprising the above additive element (Eo).   The additive element (Eo) content of the Ni-based metal oxide film (C) is 0.05 to 0.5 in terms of (Eo / Ni) atomic number ratio, according to claim 1 or 9, Shading film.   2. The light-shielding film according to claim 1, wherein the oxygen content of the Ni-based metal oxide film (C) is 0.65 to 0.85 in terms of an (O / Ni) atomic ratio.   The surface resistance value of a light shielding film is 500 ohms / square or less, The light shielding film of any one of Claim 1 thru | or 11 characterized by the above-mentioned.   The Ni-based metal film (B) and the Ni-based metal oxide film (C) have a symmetrical structure with the resin film substrate (A) as a center. The light-shielding film as described in the item.   The light shielding film according to claim 13, wherein the Ni-based metal film (B) and the Ni-based metal oxide film (C) have substantially the same film thickness and metal element composition.   A resin film (A) having a surface roughness of arithmetic average height Ra of 0.2 to 2.2 μm is supplied to the sputtering apparatus, and a film formation gas pressure of 0.1 on the resin film (A) in an inert gas atmosphere. A Ni-based metal film (B) is formed by sputtering at 2 to 1.0 Pa, and then an oxygen gas is introduced onto the Ni-based metal film (B) in an inert atmosphere, while the film-forming gas pressure is set to 0.1. By sputtering at 2 to 1.0 Pa, at least one selected from the group consisting of nickel, titanium, tantalum, tungsten, vanadium, aluminum, molybdenum, cobalt, niobium, iron, copper and zinc The method for producing a light-shielding film according to claim 1, wherein the Ni-based metal oxide film (C) is formed.   The light-shielding film in which the Ni-based metal film (B) and the Ni-based metal oxide film (C) are formed on one surface of the resin film (A) is further supplied to a sputtering apparatus, and the resin film (A) is formed by sputtering. The method for producing a light-shielding film according to claim 15, wherein a Ni-based metal film (B) and a Ni-based metal oxide film are sequentially formed on the other surface.   The method for producing a light-shielding film according to claim 15, wherein the resin film (A) is wound into a roll and set in a film transport unit of a sputtering apparatus.   The focal plane shutter blade | wing obtained by stamping the light shielding film of any one of Claims 1 thru | or 14.   The focal plane shutter blade according to claim 18, wherein the light shielding film has an overall thickness of 75 to 125 μm.

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