JP5092520B2 - Heat-resistant light-shielding film, method for producing the same, and diaphragm or light amount adjusting device using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide heat resistant/light shielding film to be used as an optical equipment component such as a shutter blade and an iris blade of a digital camera, a lens shutter, etc. and an iris blade for an optical quantity controlling iris device of a projector and excellent in a light shielding property, heat resistivity, slidability, low glossiness, and conductivity, and to provide a manufacturing method of the heat resistant/light shielding film. <P>SOLUTION: The heat resistant/light shielding film is composed of a laminated film of a resin film base material (A) having heat resistivity of &ge;200&deg;C, an N-group metallic film (B) formed one side or both sides of the resin film base material (A) by a sputtering method and having film thickness of &ge;50 nm and a low reflective oxide film (C) containing an element selected from titanium, tantalum, tungsten, vanadium, molybdenum, cobalt, niobium, iron, copper, zinc, aluminum, silicon, tin, indium, gallium, and cerium, and the surface roughness of the laminated film is 0.1 to 0.7 &mu;m. <P>COPYRIGHT: (C)2008,JPO&amp;INPIT

Description

  The present invention relates to a heat-resistant light-shielding film, a method for manufacturing the same, and an aperture or light amount adjusting device using the same, and more particularly, shutter blades or aperture blades such as apertures and lens shutters of digital cameras and digital video cameras, and projectors A heat-resistant light-shielding film excellent in light-shielding property, heat resistance, slidability, low glossiness, and conductivity, used as optical device parts such as a diaphragm blade of a diaphragm and a light amount adjusting device (also referred to as auto iris), The present invention relates to a diaphragm or a light amount adjusting device using the same.

At present, shutter blades and diaphragm blades for cameras have a high shutter speed and operate and stop in a very short time. In addition, since light is blocked by covering the front surface of a photosensitive material such as a film and an image pickup device such as a CCD, basically, light shielding is required. Furthermore, since a plurality of blades for an optical device operate while overlapping each other, lubricity is required for smooth operation. Moreover, in order to prevent the leak light between each blade | wing, it is desired that the surface reflectance is low. Depending on the usage environment, the inside of the camera may become hot, and heat resistance is required.
On the other hand, the same characteristics as digital cameras and digital video cameras are required for light-shielding films used as aperture blades for adjusting the light quantity of liquid crystal projectors, which are projection devices for viewing images such as presentations and home theaters. Therefore, characteristics superior to those of cameras are required.

In general, the light-shielding film has been put to practical use with a plastic film such as polyethylene terephthalate (PET) or a metal thin plate such as SUS, SK material, or Al as a base material. When a light shielding film made of a thin metal plate is used as a shutter blade or a diaphragm blade in a lens shutter of a camera, the metal plates rub against each other when the blade material is opened and closed, generating a large noise. Also, in a liquid crystal projector, when the image changes, it is necessary to move the blades of the light amount adjusting diaphragm device at high speed to moderate the luminance change of each image. The blades repeatedly generate rubbing noise. In order to reduce the noise, the blades are operated at a low speed. In this case, there is a problem that the light amount adjustment cannot catch up with the change in the image and the image becomes unstable.
From the viewpoints of the above problems and weight reduction, it has become the mainstream in recent years to use a plastic film as a base material instead of a metal thin plate. Further, when an insulating plastic film is used for the light shielding blade, there is a problem of dust adhesion due to electrostatic charging. Therefore, the light shielding film using the plastic substrate is also required to have conductivity. From the above circumstances, the necessary characteristics of the light shielding film are said to be high light shielding properties, heat resistance, low glossiness, slidability, conductivity, and low dust generation. In order to satisfy such properties of the light shielding film, various materials and film structures have been proposed.

For example, Patent Document 1 discloses that polyethylene black terephthalate (PET) film contains conductive black fine particles such as carbon black and titanium black in order to absorb light emitted from a lamp light source or the like in terms of light shielding properties, low glossiness, and conductivity. A light-shielding film having low gloss by impregnating a resin film such as the above to impart light-shielding properties and conductivity and further matting one or both surfaces of the light-shielding film is disclosed.
In Patent Document 2, a thermosetting resin layer containing a black pigment such as carbon black having a light-shielding property and conductivity, a lubricant, and a matting agent is applied on the surface of the resin film, and the light-shielding property, conductivity, and lubrication. And a light-shielding film imparted with low glossiness.
Patent Document 3 discloses a light shielding material in which a hard carbon film is formed on the surface of a metal blade material such as an aluminum alloy.
Patent Document 4 discloses a structure of a light shielding blade reinforced with a prepreg sheet of a thermosetting resin containing carbon fibers on both surfaces of a plastic substrate in order to increase the rigidity of the light shielding blade.

  The light shielding film is widely used as a light shielding material for optical devices such as digital cameras, digital video cameras, and liquid crystal projectors. In recent years, there has been an increasing demand for liquid crystal projectors with high image quality so that vivid high-contrast images can be enjoyed even in a bright environment such as a living room. Accordingly, since the lamp light source has a high output due to the high brightness of the image quality, the temperature in the diaphragm device for adjusting the light amount tends to be high. Since high output light is irradiated to the light shielding film for adjusting the amount of light, the light shielding film is heated and is easily deformed by heat.

A light-shielding film base material, for example, a light-shielding film based on polyethylene terephthalate is widely used because its specific gravity is light, but when the lamp light source has a high output, polyethylene terephthalate has a low thermal deformation temperature and a tensile elastic modulus. Since the mechanical strength such as the above is weak, there is a possibility that the light-shielding blade may be distorted by vibration or impact generated during running or braking.
In addition, mat processing by sandblasting is performed in order to exhibit low gloss and slidability with a light-shielding film. This treatment further has an effect of scattering the incident light to reduce the glossiness of the surface and improve the visibility. It is considered that the above treatment can prevent a decrease in slidability without increasing the contact area between the light shielding films even when the light shielding films are in contact with each other.

In digital cameras, digital video cameras, and liquid crystal projectors, the use of multiple light-shielding films as shutter blades and diaphragm blades is always close and overlapping. With a light-shielding film using an eraser, the usage environment such as temperature and humidity to which a digital camera, a digital video camera, and a liquid crystal projector are exposed is more severe. In particular, as described above, in a liquid crystal projector, the temperature in the device (light quantity adjusting device, diaphragm device) increases to around 200 ° C. due to the increase in output of the lamp light source accompanying the recent increase in image brightness. It has become to. When such a conventional light-shielding film as described above is used in such a severe environment, it is not preferable in terms of durability, such as being deformed or discolored, and there is a problem in practical use.
Furthermore, when the thermal deformation of the light-shielding film in a high heat environment at 200 ° C. or higher increases, the sliding property deteriorates due to contact between the light-shielding films, such as being unable to operate at high speed, and a fine uneven structure is formed on the surface. Even if it has a low-gloss light-shielding film, the original function of digital cameras, digital video cameras, and liquid crystal projectors can be obtained because the low-gloss deterioration occurs when the degree of rubbing due to the contact between the light-shielding films increases. There was also a possibility of being lost.

Patent Document 1 proposes a light-shielding film in which surface irregularities are formed by mat processing by sandblasting in order to express low gloss. However, in the sandblasting method, the surface roughness of the film depends on the material, particle size, discharge pressure, etc. of the shot material. Particles having a diameter of less than 1 μm remain on the film surface even after washing and cannot be completely removed. When the shot material remains, in a high heat environment where the light shielding film is exposed, the shot material and the plastic film as the base material have different thermal expansion coefficients, so the shot material falls off the film due to the difference in thermal stress, There also arises a problem that it becomes a dust generation source and adversely affects the surrounding optical components.
JP-A-1-120503 JP 4-9802 A Japanese Patent Laid-Open No. 2-116837 JP 2000-75353 A

  It is an object of the present invention to be used as a diaphragm blade of a light amount adjusting device of a liquid crystal projector that is exposed to a high temperature of 200 ° C. or higher, or a shutter blade of a shutter device of a camera that requires a heating process when incorporated. A light-shielding film with excellent properties, and also has electrical conductivity, low reflectivity (low glossiness), and lightness. Even when used at a high temperature of 200 ° C. or higher for a long time, these characteristics do not deteriorate. Another object of the present invention is to provide a heat-resistant light-shielding film free from dust generation and deformation, and a light amount adjusting diaphragm device that uses this heat-resistant light-shielding film as a diaphragm blade and is light in weight and has low power consumption during driving.

  In order to solve the above-described problems of the prior art, the present inventors used a heat-resistant resin film having fine irregularities on the surface as a base material, and formed a gas barrier film thereon as necessary, followed by sputtering. After forming a light-shielding film of Ni-based metal (B) having a specific thickness by the method, titanium, tantalum, tungsten, vanadium, molybdenum, cobalt, niobium, iron, copper are formed on the Ni-based metal film by sputtering. By laminating a low reflective metal oxide film (C) containing one or more elements selected from the group consisting of zinc, aluminum, silicon, tin, indium, gallium and cerium, A heat-resistant light-shielding film that can maintain light-shielding properties, low glossiness, slidability, color, and low reflectivity without deformation even under high heat environments can be obtained. Digital cameras, digital video cameras , It found that can be used as members for the diaphragm, such as a liquid crystal projector, and have completed the present invention.

That is, according to the first invention of the present invention, a resin film substrate (A) having a heat resistance of 200 ° C. or higher and a thickness of 50 nm or more formed on one or both surfaces of the resin film substrate (A) by a sputtering method. And a Ni-based metal film (B) having a film thickness of, and a titanium, tantalum, tungsten, vanadium, molybdenum, cobalt, niobium, iron, copper, zinc, formed on the Ni-based metal film (B) by sputtering. A layered film of a low-reflective oxide film (C) containing one or more elements selected from the group consisting of aluminum, silicon, gallium and cerium, and the film thickness of the Ni-based metal film (B) is 50 to 250 nm, the thickness of the oxide film (C) is 5 to 240 nm, and the surface roughness of the laminated film is 0.1 to 0.7 μm (arithmetic average height Ra). Resistance Shielding film is provided.

According to the second invention of the present invention, in the first invention, the resin film substrate (A) is one or more organic materials selected from polyimide, aramid, polyphenylene sulfide, or polyether sulfone. A heat-resistant light-shielding film is provided which is made of resin and has a surface roughness of 0.2 to 0.8 μm (arithmetic average height Ra).
According to the third invention of the present invention, in the first invention, the Ni-based metal film (B) is composed mainly of nickel, titanium, tantalum, tungsten, vanadium, molybdenum, cobalt, niobium, iron, There is provided a heat-resistant light-shielding film, which is a nickel-based alloy film containing one or more additive elements selected from the group consisting of copper, zinc, aluminum, and silicon.
According to a fourth invention of the present invention, in any one of the first to third inventions, the laminated film has a surface resistance value of 1 × 10 ⁴ Ω / □ or less. Is provided.
Furthermore, according to a fifth aspect of the present invention, there is provided a heat resistant light-shielding film according to the first to fourth aspects, wherein the laminated film has a light reflectance of 5% or less at a wavelength of 380 to 780 nm. Is done.
According to the sixth invention of the present invention, in any one of the first to fifth inventions, the Ni-based metal film (B) and the oxide film (C) are formed on both surfaces of the resin film substrate (A). A heat-resistant light-shielding film is provided, which has a laminated film formed and has a symmetrical structure with a film substrate as a center.

According to the seventh invention of the present invention, in any one of the first to sixth inventions, the metal oxide formed by a sputtering method at the interface between the resin film substrate (A) and the metal film (B). A heat-resistant light-shielding film is provided in which a material film is interposed as a gas barrier film (D).
Furthermore, according to an eighth aspect of the present invention, in the seventh aspect , the gas barrier film is made of titanium, tantalum, tungsten, vanadium, molybdenum, cobalt, niobium, iron, aluminum, silicon, and nickel. There is provided a heat-resistant light-shielding film, which is an oxide film containing as a main component one or more elements selected from the above.
According to the ninth invention of the present invention, in the seventh or eighth invention, the gas barrier films (D) formed on both surfaces of the resin film substrate (A), the metal films (B), and the oxidation The heat-resistant light-shielding film is provided in which the material films (C) have substantially the same metal element composition.
Further, according to the tenth aspect of the present invention, in any one of the first 7-9, gas barrier layer (D) with each other is formed on both surfaces of the resin film substrate (A), a metal film (B) with each other And the oxide film (D) have substantially the same metal element composition, and a heat-resistant light-shielding film is provided.
On the other hand, according to the eleventh aspect of the present invention, in any one of the first to sixth aspects, the uneven surface having a surface roughness of one or both sides of 0.2 to 0.8 μm (arithmetic average height Ra) is provided. The resin film substrate (A) having the above is supplied to a sputtering apparatus, and a Ni-based metal film (B) is formed on the uneven surface of the resin film substrate (A) by sputtering using a metal film forming target, Next, titanium, tantalum, tungsten, vanadium, molybdenum, cobalt, niobium, and the like are formed on the Ni-based metal film (B) by reactive sputtering using an oxide film forming target and oxygen gas introduced into the sputtering gas. Forming an oxide film (C) containing one or more elements selected from the group consisting of iron, copper, zinc, aluminum, silicon, gallium and cerium That the production method of the heat-resistant light-shading film is provided.

According to a twelfth aspect of the present invention, there is provided the method for producing a heat-resistant light-shielding film according to the seventh aspect, wherein the sputtering gas pressure is 0.2 to 1.0 Pa.
According to the thirteenth aspect of the present invention, there is provided the method for producing a heat-resistant light-shielding film according to the eleventh or twelfth aspect , wherein the resin film substrate temperature during sputtering is 180 ° C. or higher. The
According to a fourteenth aspect of the present invention, in any one of the first to thirteenth aspects, the heat-resistant light-shielding film on which the Ni-based metal film (B) and the oxide film (C) are formed, , And supply to the sputtering apparatus, the Ni-based metal film (B) on the back surface of the resin film substrate (A) by sputtering, and titanium, tantalum, tungsten, vanadium, molybdenum, cobalt, niobium, iron, copper, zinc, aluminum, There is provided a method for producing a heat-resistant light-shielding film, comprising sequentially forming an oxide film (C) containing one or more elements selected from the group consisting of silicon, gallium and cerium.
According to the fifteenth aspect of the present invention, in the seventh to tenth aspects, the resin film having an uneven surface having a surface roughness of 0.2 to 0.8 μm (arithmetic average height Ra) on one or both sides. A base material (A) is supplied to a sputtering apparatus, a gas barrier film (D) is first formed on the uneven surface of the resin film base material (A) by sputtering using a gas barrier film forming target, and then a metal film ( B) and the oxide film (C) are formed in order, and a method for producing a heat-resistant light-shielding film is provided.
According to a sixteenth aspect of the present invention, in the fifteenth aspect , the gas barrier film forming target and the metal film forming target, or the gas barrier film forming target and the oxide film forming target are each There is provided a method for producing a heat-resistant light-shielding film, wherein each film is formed using the same material.
According to the seventeenth invention of the present invention, in any one of the eleventh to sixteenth inventions, the resin film substrate (A) is wound into a roll shape and set in the film transport section of the sputtering apparatus. A method for producing a heat-resistant light-shielding film is provided.
Furthermore, according to the eighteenth aspect of the present invention, in any one of the eleventh to sixteenth aspects, the resin film substrate being formed is sputtered in a floating state in the film forming chamber without being cooled. A method for producing a heat-resistant light-shielding film is provided.
On the other hand, according to the nineteenth aspect of the present invention, there is provided a diaphragm having excellent heat resistance produced by processing the heat-resistant light-shielding film according to any one of the first to tenth aspects.
Furthermore, according to the twentieth aspect of the present invention, there is provided a light amount adjusting device using the heat-resistant light-shielding film of any one of the first to tenth aspects as a blade material.

The heat-resistant light-shielding film of the present invention comprises a heat-resistant resin film substrate having a heat resistance of 200 ° C. or higher, a Ni-based metal film (hereinafter also simply referred to as a metal film) having a specific thickness by sputtering, titanium, Low reflective oxide containing one or more elements selected from the group consisting of tantalum, tungsten, vanadium, molybdenum, cobalt, niobium, iron, copper, zinc, aluminum, silicon, tin, indium, gallium and cerium A film (hereinafter also simply referred to as an oxide film) is formed. Therefore, since the heat-shielding light-shielding metal film and the low-reflective oxide film form a dense film structure, the surface wear resistance and friction compared to the light-shielding film obtained by the conventional coating process. Excellent in conductivity and conductivity.
In this heat-resistant light-shielding film, a low-reflective oxide film that is the outermost surface layer is laminated on the metal film, so that the high reflectance of the metal film can be reduced, and the surface roughness of the laminated film is 0.1. The light reflectance at a wavelength of 380 to 780 nm is low reflection (low glossiness) of 5% or less, which is also contributed by being -0.7 μm (arithmetic average height Ra).
The heat-resistant light-shielding film of the present invention is reduced in weight because it uses a resin film as a base material compared to a conventional light-shielding blade using a heat-resistant light-shielding film with a heat-resistant paint applied to a metal foil plate, and is mounted on a diaphragm blade or the like This improves the slidability and further reduces the size of the drive motor, leading to lower costs.
Furthermore, it can be used as a heat-resistant light-shielding film in which a metal film and an oxide film are formed only on one side of the resin film substrate, and an adhesive is applied to the resin film side where the metal film and the oxide film are not formed. In a lens barrel such as a camera or projector, a low reflection surface can be formed by sticking to a wall surface of a member indispensable for low reflection and low gloss.
In addition, when the metal film and the oxide film are formed by sputtering, the film structure can be symmetrical with the heat-resistant resin film as the center, and the light-shielding film is not deformed by the film stress during the film formation. Excellent in properties.
Further, by optimizing the film formation conditions by the sputtering method of the light-shielding metal film and the low-reflective oxide film of the present invention, the film can be made into a dense and highly adhesive film, which is about 200 ° C. Even when exposed to a high heat environment, the film does not peel off. Since the dense and hard outermost oxide film is covered, the film does not peel off during the operation of the heat-resistant light-shielding film. Matting treatment of the base film, specifically, the above-mentioned, which can maintain high adhesion even at high temperature even if the shot material remains on the film surface without being removed during the film surface treatment by the sandblast method Since the dense laminated film is covered, dust due to dropping of the shot material or peeling of the film does not occur even at high temperatures.
Therefore, the heat-resistant light-shielding film of the present invention is particularly useful as a diaphragm blade material for a light amount adjusting device of a liquid crystal projector that is required to have heat resistance, and has a heating process when attached. Since it can also be used as a shutter blade material of a shutter device such as the above, it is extremely useful industrially.
Furthermore, the light quantity adjusting device using the heat-resistant light-shielding film of the present invention as the diaphragm blade material is lighter than the conventional heat-resistant light quantity adjusting diaphragm device using a metal thin plate as the blade material. Reduction of power consumption when driving the blades can be realized. Accordingly, the drive motor can be downsized, and the light amount adjusting diaphragm device itself can be downsized. Therefore, it can be said to be extremely useful industrially.

  Hereinafter, the heat-resistant light-shielding film of the present invention, a method for producing the same, and a diaphragm or light amount adjusting device using the same will be described with reference to FIG.

1. Heat-resistant light-shielding film The heat-resistant light-shielding film of the present invention comprises a resin film substrate (A) having a heat resistance of 200 ° C. or higher and a film of 50 nm or more formed on one or both surfaces of the resin film substrate (A) by a sputtering method. Ni-based metal film (B) having a thickness, and titanium, tantalum, tungsten, vanadium, molybdenum, cobalt, niobium, iron, copper, zinc, aluminum formed on the Ni-based metal film (B) by sputtering. It consists of a laminated film of a low reflective oxide film (C) containing one or more elements selected from the group consisting of silicon, gallium and cerium, and the Ni-based metal film (B) has a film thickness of 50 to 50 250 nm, the thickness of the oxide film (C) is 5 to 240 nm, and the surface roughness of the laminated film is 0.1 to 0.7 μm (arithmetic average height Ra). To do.

FIG. 1 is a schematic diagram showing the configuration of an example of a heat-resistant light-shielding film according to the present invention. The light-shielding film of the present invention includes a resin film 1 as a base material, a Ni-based metal film 2 formed on the surface thereof, and titanium, tantalum, tungsten, vanadium, molybdenum, cobalt, niobium, and iron formed thereon. , Copper, zinc, aluminum, silicon, gallium and cerium, and a laminated film with a low reflective oxide film 3 containing one or more elements selected from the group consisting of copper, zinc, aluminum, silicon, gallium and cerium.
The laminated film has a surface roughness of 0.1 to 0.7 μm (arithmetic average height Ra) . The thickness is preferably 0.2 to 0.7 μm, more preferably 0.3 to 0.6 μm. If the surface roughness of the laminated film is less than 0.1 μm, low gloss cannot be obtained, and if the surface roughness of the laminated film exceeds 0.7 μm, surface defects of the laminated film are likely to occur and sufficient light shielding properties ( This is not preferable in that a transmittance of 0% cannot be obtained.

  Although the thickness of the resin film 1 is not specifically limited, For example, it is desirable that it is the range of 10-125 micrometers. When the thickness is less than 10 μm, the film itself is poorly handled during the production of the light-shielding film, and surface defects such as scratches and creases are easily attached to the film, making it difficult to produce with a high yield. This is because if the thickness is larger than 125 μm, it is impossible to mount a plurality of light shielding blades on a shutter device or a light amount adjusting diaphragm device that is becoming smaller.

  The light-shielding Ni-based metal film (metal film) has a thickness of 50 nm or more. If the thickness is less than 50 nm, light passage through the film occurs and the light shielding function is not sufficient, which is not preferable. However, when the film thickness is increased, the light shielding property is improved. However, if the thickness exceeds 250 nm, the manufacturing cost is increased due to an increase in material cost and film formation time, and the stress of the film is increased and the film is easily deformed. In consideration of sufficient light shielding properties (transmittance of 0%), low film stress, and low manufacturing cost, the thickness of the metal film is preferably 50 to 250 nm. Contains one or more elements selected from the group consisting of low reflective titanium, tantalum, tungsten, vanadium, molybdenum, cobalt, niobium, iron, copper, zinc, aluminum, silicon, tin, indium, gallium and cerium The metal oxide film (oxide film) can reduce the reflectance in the visible region by setting the film thickness to 5 to 240 nm.

  One or more elements selected from the group consisting of the Ni-based metal film and titanium, tantalum, tungsten, vanadium, molybdenum, cobalt, niobium, iron, copper, zinc, aluminum, silicon, tin, indium, gallium and cerium. The low reflective oxide film to be contained may be formed on one side of the resin film substrate, but is preferably formed on both sides. When formed on both surfaces, it is more preferable that the composition and film thickness of the metal films and oxide films on each surface are symmetrical with respect to the film substrate. Since the thin film formed on the substrate gives stress to the substrate, it causes deformation. Although deformation due to stress may be observed even immediately after film formation, the deformation becomes large and becomes prominent particularly when heated to about 200 ° C. However, as described above, the metal film formed on both surfaces of the substrate and the low-reflective oxide film are made of the same material and have a symmetrical structure with the substrate as the center, thereby balancing the stress even under heating conditions. Is maintained and it is easy to realize a flat heat-resistant light-shielding film.

(A) Resin film substrate The resin film which is the substrate of the heat-resistant light-shielding film of the present invention has a fine arithmetic average height Ra of 0.2 to 0.8 μm, particularly 0.3 to 0.7 μm on the surface thereof. It preferably has an uneven structure. 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. When Ra is smaller than 0.2 μm, the adhesion of the metal film formed on the film surface cannot be obtained, and sufficient low glossiness and low reflectivity cannot be obtained. On the other hand, if Ra exceeds 0.8 μm, the unevenness of the film surface is so large that the metal film cannot be formed in the recess, and the film thickness of the metal film can be obtained by covering the film surface and obtaining sufficient light shielding properties. Is undesirably high in cost.

  The resin film used as the substrate may be made of a transparent resin or a colored resin kneaded with a pigment, but must have a heat resistance of 200 ° C. or higher. Here, a film having a heat resistance of 200 ° C. or higher is a film having a glass transition point of 200 ° C. or higher, and a material having no glass transition point is not altered at a temperature of 200 ° C. or higher. means. In view of mass productivity, the resin material is preferably a flexible material that enables roll coating by sputtering.

  The heat-resistant resin film includes a film composed of one or more organic resin materials selected from polyimide (PI), aramid (PA), polyphenylene sulfide (PPS), or polyether sulfone (PES). Although it is preferable, it is not limited to these as long as it has heat resistance of 200 ° C. or higher. Among them, the polyimide film has the highest heat resistant temperature and is a particularly preferable film.

  The resin film surface is subjected to surface treatment to form irregularities. Here, the surface treatment can be obtained, for example, by performing nanoimprinting or mat treatment using sand as a shot material, but is not limited to such a treatment method. Matting processing using shot material can form unevenness on the film surface while transporting the film, but the optimal Ra value unevenness depends on the film transport speed during mat processing, the type and size of shot material Therefore, the surface treatment is performed so that the arithmetic average height Ra value of the film surface is 0.2 to 0.8 μm by optimizing these conditions. The film after the mat treatment is washed to remove the shot material and then dried. When a metal film and a low-reflective oxide film are formed on both sides of the film, both sides of the film are matted.

(B) Metal film The heat-resistant light-shielding film of the present invention is characterized by having heat resistance that can withstand even in a high heat environment of 200 ° C. This is because a metal film and a low-reflective oxide film obtained at a temperature higher than the above temperature by sputtering are highly dense and have good oxidation resistance, and good adhesion between the film and the metal film.

In general, when a metal film is oxidized, the transparency increases. Therefore, the oxidation resistance of the metal film to be a light shielding film is important. Further, depending on the type of metal, the metal film may be a material that melts at 200 to 250 ° C. Therefore, it is important that the metal film serving as the light shielding film is a high melting point material of 300 ° C. or higher. The material of the metal film used for the heat-resistant light-shielding film of the present invention is preferably a nickel-based material having excellent oxidation resistance. Specifically, the metal film may be pure nickel, but from the group consisting of nickel, titanium, tantalum, tungsten, vanadium, molybdenum, cobalt, niobium, iron, copper, zinc, aluminum, and silicon. A nickel-based alloy film to which one or more selected elements are added is preferable. The metal film to which the above elements are added is less likely to be oxidized than pure nickel.
When a Ni-based metal film containing these elements is formed on a resin film such as polyimide by a sputtering method, high adhesion can be obtained. Moreover, in order to further improve heat resistance and corrosion resistance, the Ni-based metal film of the above element may be an alloy obtained by adding an element other than the above metal element or an intermetallic compound. .

Further, the film formation speed in sputtering film formation using a nickel-based target is characterized by being faster than sputtering film formation using other metal targets, and this aspect is also advantageous for productivity. For example, the deposition rate of a nickel film by direct current 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 material of the Ni-based metal film may contain carbon and nitrogen in addition to the above metal elements. Carbon and nitrogen can be introduced into the Ni-based metal film by introducing an additive gas such as hydrocarbon gas and nitrogen gas into the sputtering gas when forming the metal film, respectively. However, these elements can be introduced even if carbon and nitrogen are contained in the target without using the above additive gas. In particular, when the metal film contains carbon or nitrogen, it is useful because the heat resistance can be further improved.

Therefore, the nickel-based metal film material of the heat-resistant light-shielding film of the present invention includes nickel titanium carbide, nickel tantalum carbide, nickel tungsten carbide, nickel molybdenum carbide, nickel niobium carbide, nickel iron carbide, nickel copper produced by the above method. Carbide, nickel aluminum carbide, nickel silicon carbide, nickel titanium nitride, nickel tantalum nitride, nickel tungsten nitride, nickel molybdenum nitride, nickel niobium nitride, nickel iron nitride, nickel copper nitride, nickel aluminum nitride, Carbides and nitrides such as nickel silicon nitride are also metal film materials that exhibit sufficient light shielding properties and heat resistance, and are also included because they exhibit high adhesion to resin films. Further, the nickel-based metal film material of the heat-resistant light-shielding film of the present invention includes solid solutions and compounds of these carbides and nitrides, and solid solutions and compounds of these carbides and / or nitrides and the above metal elements for the same reason. . In addition, it is preferable that the metal film of the present invention contains as little oxygen as possible in order to maintain high adhesion to the resin film and high light shielding properties. However, oxygen remaining in the sputtering gas is contained in the metal film during film formation, or even if oxygen or moisture contained in the film is diffused and taken into the metal film, It does not matter as long as it does not impair high light-shielding properties and high adhesion with the resin film. The oxygen content in the metal film is desirably 5 atomic% or less, particularly 3 atomic% or less, based on the metal element in order to maintain adhesion with the resin film.
In addition, the metal film of the heat-resistant light-shielding film of the present invention is composed of a laminated film of a plurality of types of metal films having different compositions (content and type of metal element, carbon content, nitrogen content, oxygen content). It doesn't matter.

  The metal film has a thickness of 50 to 250 nm. When the film thickness is less than 50 nm, the light shielding property may be insufficient, and the adhesion with the film may be insufficient. When the film thickness exceeds 250 nm, the adhesion with the film and the stackability of the oxide film are sufficient. However, it is not preferable in terms of economy.

About adhesion, it is difficult to obtain high adhesion between a resin film substrate that is organic and a metal film that is inorganic. This is because when the adhesion at the interface between the resin film substrate and the metal film is insufficient, film peeling is likely to occur due to a difference in thermal expansion between the resin film substrate and the metal film in a high heat environment of 200 ° C. .
In order to avoid such film peeling due to the difference in thermal expansion, it is necessary to maintain high adhesion between the resin film substrate and the film, but the metal film of the present invention is made of titanium, tantalum, tungsten, vanadium, molybdenum, It is effective to use a nickel-based metal film containing one or more additive elements selected from the group consisting of cobalt, niobium, iron, copper, zinc, aluminum, and silicon. The surface of the resin film has an oxygen functional group, and an appropriate amount of titanium, tantalum, tungsten, vanadium, molybdenum, cobalt, niobium, iron, copper, zinc, aluminum, and silicon is contained in the metal film of the present invention. An element that easily binds to oxygen, such as, is included, and a chemical bond is formed with a functional group of oxygen on the film surface, thereby enhancing the adhesion between the film and the metal film.
Moreover, the thin film of another material may exist in the very thin (for example, 1-10 nm) to such an extent that adhesiveness is not impaired at the interface of the metal film of the said metal material, and a resin film.

(C) Oxide film The heat-resistant light-shielding film of the present invention has a low-reflective oxide film. The metal film formed on the resin film substrate has a high reflectance, but by laminating a low-reflective oxide film on the metal film, the reflectance of the heat-resistant light-shielding film at a wavelength of 380 to 780 nm is 7% or less. Can be reduced to The low-reflective oxide film may be composed of a single layer or layers having different oxygen contents, types of constituent elements, and contents. Further, the low-reflective oxide film laminated on the metal film may be colored.

The low reflective oxide film of the present invention is selected from the group consisting of titanium, tantalum, tungsten, vanadium, molybdenum, cobalt, niobium, iron, copper, zinc, aluminum, silicon, tin, indium, gallium and cerium. An oxide film containing one or more elements is preferable. The oxide film is excellent in heat resistance and other corrosion resistance under a high heat environment. Specifically, the oxide film is selected from the group consisting of titanium, tantalum, tungsten, vanadium, molybdenum, cobalt, niobium, iron, copper, zinc, aluminum, silicon, tin, indium, gallium and cerium. It may be an oxide composed of only one element selected from the group consisting of titanium, tantalum, tungsten, vanadium, molybdenum, cobalt, niobium, iron, copper, zinc, aluminum, silicon, tin, indium, gallium and cerium. An oxide film containing two or more elements selected from the group may be used. Further, a compound layer containing some or all of the components of these films may be formed at the interface between these oxide films and metal films.
The oxide film contains at least one element selected from the group consisting of titanium, tantalum, tungsten, vanadium, molybdenum, cobalt, niobium, iron, copper, zinc, aluminum, silicon, tin, indium, gallium, and cerium. This is because these elements are easy to form a passivity, and therefore have excellent corrosion resistance in addition to heat resistance. In addition, an oxide film containing an element such as titanium, tantalum, tungsten, vanadium, molybdenum, cobalt, niobium, iron, copper, zinc, aluminum, silicon, tin, indium, gallium, and cerium has excellent heat resistance. Also, since it has high wear resistance and toughness, there is an advantage in operating as a light shielding blade.

  The oxide film may contain carbon and nitrogen in addition to the above metal elements. When carbon and nitrogen are included in the oxide film, the refractive index can be adjusted and low reflectivity can be easily realized. In addition, when the oxide film is made of an oxide material that introduces oxygen vacancies as much as possible so that it does not become a metal film and has a low transmittance in the visible region (for example, a single film has a transmittance of 10 to 60%). It is preferable because low reflectivity is easily realized. The heat-resistant light-shielding film of the present invention using such an oxide film can have a light reflection of 2% or less, 1% or less, or 0.5% or less at a wavelength of 380 to 780 nm. The oxide film may be formed of a stacked film of a plurality of types of oxide films having different compositions (oxygen content, carbon content, nitrogen content, metal element content). By using an oxide film with a different composition and different refractive index and extinction coefficient, a stronger antireflection effect can be realized and low reflectivity can be realized. A film can be obtained.

The film thickness of the oxide film has a 5～240Nm. The reflectance in the visible range can be reduced by setting the thickness to 20 to 240 nm, more preferably 30 to 200 nm. If the film thickness is less than 5 nm, the reflectivity and glossiness may not be lowered sufficiently.

In addition, the heat-resistant light-shielding film of the present invention can have a high reflection property of heat ray light in order to avoid as much as possible a temperature rise due to heat ray irradiation. In this case, contrary to the above, the oxide film uses an oxide material having as high a transmittance as possible in the visible region to the near infrared region, and suppresses the absorption of heat rays in the oxide film as much as possible. The high reflection characteristic of the heat ray by the metal film is used. In addition, taking into account the refractive index of such an oxide film, the thickness of the oxide film is optimized, and the near-infrared reflected light at the oxide film / metal film interface and It is more preferable that near-infrared reflected light strengthen each other to realize high reflection characteristics. The heat-resistant light-shielding film having the high-reflective property of the heat ray having the above-described configuration can exhibit an appropriate reflectivity of 3 to 7% in the maximum reflectivity in the visible range. When the reflectance is high and 10% or more, the reflected light becomes stray light and has an adverse effect, so 7% or less is preferable. The heat-resistant light-shielding film having such a configuration is inferior in blackness, but exhibits red, purple, blue, ocher, etc. according to the wavelength balance of reflected light.
Moreover, in the heat-resistant light-shielding film of the present invention in which the metal film and the oxide film are laminated on both sides of the resin film, the blackness and the reflectance are different on both sides by using oxide films having different transmittances on each side It is also effective to have a configuration. For example, when the heat-resistant light-shielding film of the present invention is used as a blade material near a projector lamp, the film surface side irradiated with lamp light places the highest priority on avoiding a temperature rise due to light irradiation. Because the surface with high reflection characteristics of visible to near-infrared light faces each other and the opposite side of the lamp faces the lens unit, reflection of visible light is disliked as stray light. It is effective to face a surface having low reflectivity. In that case, it is effective to use a low blackness and high reflectivity surface facing the lamp side and a low black and low reflectivity surface facing the lamp.
Here, the plastic film generally has an insulating property and is likely to generate static electricity. However, if the insulating light-shielding film is used as a light-shielding blade, static electricity is generated and the blades are electrostatically adsorbed. There is a case. In order for the blades not to adsorb, it can be said that the light shielding film needs to be conductive.

The material of the film used for the heat-resistant light-shielding film of the present invention includes, as a specific metal film, nickel as a main component, titanium, tantalum, tungsten, vanadium, molybdenum, cobalt, niobium, iron, copper, zinc, aluminum, and This is a nickel-based alloy film to which one or more elements selected from the group consisting of silicon are added. Examples of oxide films include titanium, tantalum, tungsten, vanadium, molybdenum, cobalt, niobium, iron, copper, and zinc. , Aluminum, silicon, tin, indium, gallium, and cerium, the oxide film contains one or more elements selected from the group consisting of aluminum, silicon, tin, indium, gallium, and cerium, and therefore has conductivity and a surface resistance of 10 ¹³ Ω / □ (Read ohms per square and) compared with the light-shielding film such as the is a resin coating system described above, the surface resistivity 1 × 10 ⁴ Ω / □ or less Can be small with the bottom.

  In the heat-resistant light-shielding film of the present invention, a nickel-based material having excellent conductivity for the metal film, and a highly conductive material for the oxide film (for example, titanium oxide, tungsten oxide, vanadium oxide, molybdenum oxide, niobium oxide, iron oxide, By selecting copper oxide, zinc oxide, tin oxide, indium oxide, gallium oxide, cerium oxide, etc., the surface resistance value can be 800Ω / □ or less, preferably 100Ω / □ or less, and further 10Ω / □ or less. it can.

In the heat-resistant light-shielding film of the present invention, other thin films (for example, fluorine-containing organic films, carbon films, diamond-like carbon films, etc.) having lubricity and low friction properties are thinly formed on the surface of the oxide film. Even if it is applied and used, it does not matter if the characteristics of the present invention are not impaired.
In the heat-resistant light-shielding film of the present invention, the light reflectance of the laminated film can be 5% or less at a wavelength of 380 to 780 nm. When the light reflectance exceeds 5% at a wavelength of 380 to 780 nm, it cannot be preferably used as a diaphragm blade of a shutter device or a light amount adjusting diaphragm device.

(D) Gas barrier film Usually, a resin film substrate such as polyimide contains a large amount of oxygen and moisture. These gases in the polyimide are removed by heat treatment or the like before film formation. However, a heat-resistant light-shielding film manufactured by forming a metal film and an oxide film without being sufficiently removed can release oxygen and moisture from the resin film when placed in a high heat environment of around 250 ° C. Oxygen enters part of the membrane. Since the metal film into which oxygen has entered has different optical constants, the color of the heat-resistant light-shielding film changes. In addition, even in a heat-resistant light-shielding film manufactured by sufficiently venting before film formation, if the heat-resistant light-shielding film is placed in an environment of a constant temperature and humidity test (eg, 85 ° C., 90% RH, 1000 hours) Water and oxygen enter from the side of the film, oxygen enters a part of the metal film on the resin film side, and the color changes due to the same factors. In order to avoid such color change, the present invention proposes forming a metal oxide film as a gas barrier film at the interface between the resin film substrate and the metal film by a sputtering method.

  As the gas barrier film, for example, an oxide film mainly containing one or more elements selected from the group consisting of titanium, tantalum, tungsten, vanadium, molybdenum, cobalt, niobium, iron, aluminum, silicon, and nickel is effective. is there. Among these gas barrier films, a film having oxygen vacancies has a higher film density than a stoichiometric composition, so that the passage of gas released from the film can be more effectively prevented. It is effective if the gas barrier film is formed to have a thickness of about 5 to 30 nm.

2. Manufacturing method of heat-resistant light-shielding film The manufacturing method of the heat-resistant light-shielding film of the present invention supplies a resin film substrate (A) having a surface roughness with an arithmetic average height Ra of 0.2 to 0.8 μm to a sputtering apparatus, Using a metal film formation target, sputtering is performed at a film substrate temperature of 180 ° C. or higher under an inert gas atmosphere to form a Ni-based metal film (B) on the resin film substrate (A). Sputtering is performed while introducing oxygen gas into an inert gas atmosphere using a target for forming an oxide film, and titanium, tantalum, tungsten, vanadium, molybdenum, cobalt, niobium, and iron are formed on the Ni-based metal film (B). Forming an oxide film (C) containing one or more elements selected from the group consisting of copper, zinc, aluminum, silicon, tin, indium, gallium and cerium Characterized in that to obtain a heat-shielding film Te.

In the heat-resistant light-shielding film of the present invention, a Ni-based metal film is formed by a sputtering method on the surface of the resin film substrate, and low-reflective titanium, tantalum, tungsten, vanadium, molybdenum, An oxide film containing one or more elements selected from the group consisting of cobalt, niobium, iron, copper, zinc, aluminum, silicon, tin, indium, gallium and cerium is formed by sputtering. The oxide film is more preferably set to a film thickness that exhibits an antireflection effect. In other words, visible light incident on the surface of the heat-resistant light-shielding film is reflected at the interface between the oxide film and air and at the interface between the metal film and the oxide film, but these reflected lights interfere with each other when they enter the atmosphere. It is preferable that the film thickness of the oxide film generate a phase difference that cancels out because it achieves extremely low reflectivity. In the present invention, since the metal film and the low-reflectivity oxide film are formed by sputtering, the film has better denseness than the ink coating method or vacuum deposition method, and the base (substrate or film). It has the characteristic that adhesiveness is good.
This property is remarkable when the heat-resistant light-shielding film is used in a high heat environment of 200 ° C. When formed by ink coating or vacuum deposition, film peeling and color change due to oxidation of the film can be seen, but such a fear may occur when the film is formed by sputtering as in the present invention. Absent.

  In the present invention, the heat-resistant light-shielding film is produced by forming a light-shielding metal film and a low-reflective 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 a sputtering gas pressure of argon or the like (about 10 Pa or less), a base material is used as an anode and a sputtering target as a raw material for a film is used as a cathode, and glow plasma is generated therebetween to generate argon plasma. In this method, the argon cation in the plasma is collided with the sputtering target of the cathode, the particles of the sputtering target component are blown off, and the particles are deposited on the substrate to form a film.

  The sputtering method is classified according to the method of generating argon plasma. A method using high frequency plasma is a high frequency (RF) sputtering method, and a method using direct current plasma is a direct current (DC) sputtering method. The magnetron sputtering method is a method in which a magnet is arranged on the back side of a sputtering target, argon plasma is concentrated directly on the sputtering target, and a film is formed by increasing the collision efficiency of argon ions even at a low gas pressure.

  In order to form the metal film and the oxide film, for example, a winding type sputtering apparatus shown in FIG. 2 can be used. In this apparatus, a roll-shaped resin film substrate 1 is set on an unwinding roll 4, and after the vacuum tank 6 is evacuated by a vacuum pump 5 such as a turbo molecular pump, the film 1 unloaded from the unwinding roll 4 is removed. In the middle, the structure is such that it is taken up by the take-up roll 8 through the surface of the cooling can roll 7. A magnetron cathode 9 is installed on the opposite side of the surface of the cooling can roll 7, and a target 10 serving as a film raw material is attached to this cathode. Note that the film transport unit including the unwinding roll 4, the cooling can roll 7, the winding roll 8, and the like is separated from the magnetron cathode 8 by the partition wall 11.

  As the target, a metal film forming target and an oxide film forming target are used. The metal film forming target is a metallic target made of Ni metal or Ni-based alloy. Further, in order to include carbon and / or nitrogen in the metal film, the metal target for forming the metal film may include carbon and / or nitrogen, and the above metal carbide or nitride metal target may be used. You may use. On the other hand, the oxide film forming target is selected from the group consisting of titanium, tantalum, tungsten, vanadium, molybdenum, cobalt, niobium, iron, copper, zinc, aluminum, silicon, tin, indium, gallium and cerium. It is a metal target or an oxide target containing more than one kind of element. In addition, in order to include carbon and / or nitrogen in the oxide film, the metal target or oxide target for forming the oxide may include carbon and / or nitrogen, and the above-described metal carbide or nitride. The metal target may be used.

  First, the roll-shaped resin film substrate 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 substrate 1 is supplied from the unwinding roll 4, and while being taken up by the take-up roll 8 through the surface of the cooling can roll 7 on the way, between the cooling can roll 7 and the cathode. It discharges and forms into a film on the resin film base material 1 closely_contact | adhered and conveyed by the cooling can roll surface. The resin film substrate is desirably heated at a temperature of 200 ° C. or higher and dried before sputtering. In addition, a resin film substrate (A) having an uneven surface with a surface roughness of 0.2 to 0.8 μm (arithmetic average height Ra) on one or both sides is supplied to a sputtering apparatus, and a target for gas barrier film formation is used. Then, it is preferable to first form a gas barrier film (D) on the uneven surface of the resin film substrate (A) by sputtering.

  In the heat-resistant light-shielding film of the present invention, the metal film layer is formed on the resin film substrate by a radio frequency (RF) or direct current (DC) magnetron sputtering method using a sputtering target of Ni metal or Ni-based alloy, for example, in an argon atmosphere. A film is formed.

  Since pure nickel material is usually a ferromagnetic material, when the metal film layer is formed by DC magnetron sputtering, it is from a magnet placed on the back surface of the sputtering target for acting on the plasma between the sputtering target and the substrate. The magnetic field is shielded by the nickel target material and the magnetic field leaking to the surface becomes weak, 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, if 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 elements selected from titanium, tantalum, tungsten, vanadium, molybdenum, cobalt, niobium, iron, copper, zinc, aluminum, and silicon with nickel as a main component are added. By using the Ni-based alloy material as a target, ferromagnetism is weakened, the above problems can be avoided, and a metal alloy film having the above composition can be formed.

  The gas pressure at the time of forming the metal film varies depending on the type of the apparatus and cannot be generally specified, but is preferably 1.0 Pa or less, for example, 0.2 to 1.0 Pa. As a result, even if a small amount of shot material remains on the resin film substrate, the film does not peel off due to a difference in thermal expansion of the shot material, the metal film, and the low-reflective oxide film in a high heat environment at 200 ° C. When the gas pressure at the time of film formation exceeds 1.0 Pa, the metal film grains become coarse and the film quality is not high, so that the adhesion with the resin film substrate becomes weak and the film is peeled off. If the gas pressure during film formation is less than 0.2 Pa, the gas pressure is low, so that argon plasma in the sputtering method becomes unstable, and the film quality of the formed film may deteriorate.

Furthermore, it is desirable that the temperature of the resin film substrate during film formation is at least 180 ° C. or higher, particularly 180 to 220 ° C. Thereby, a dense heat-resistant light-shielding film having excellent adhesion to a film having a heat resistance of 200 ° C. or higher is obtained. When the temperature of the resin film substrate during film formation is less than 180 ° C., the adhesion between the metal film and the resin film in a heat resistance test at 200 ° C. or more is not preferable. However, when such heat resistance is not required, the metal film can be formed at less than 180 ° C. The film thickness of the metal film is controlled by the film conveyance speed during film formation and the input power to the target.
In addition, the resin film substrate is naturally heated from the plasma during film formation. By adjusting the gas pressure, the input power to the target, and the film conveyance speed, it is easy to maintain the temperature of the substrate during film formation at 180 ° C. or higher by natural heating. The lower the gas pressure, the higher the input power, and the slower the film transport speed, the higher the heating temperature by natural heating from the plasma. The temperature of the substrate during film formation can also be measured with a radiation thermometer, and a thermolabel is attached to the film surface in advance, and the temperature reached after seeing the color change of the label after film formation Can know.

  After the metal film is formed, the metal film is selected from the group consisting of titanium, tantalum, tungsten, vanadium, molybdenum, cobalt, niobium, iron, copper, zinc, aluminum, silicon, tin, indium, gallium and cerium. An oxide film containing one or more elements is formed. The low-reflective oxide layer can be formed by, for example, a radio frequency (RF) or direct current (DC) magnetron sputtering method in an argon and oxygen gas atmosphere using a metal target of a metal component in the oxide film. . In addition, as described above, an oxide target containing a metal component of an oxide film is used to form a radio frequency (RF) or direct current (DC) magnetron sputtering method using an argon gas atmosphere or a mixed gas atmosphere of argon and oxygen. be able to. Regardless of which target is used, it is preferable to use reactive sputtering using a mixed gas atmosphere of argon and oxygen. The content of oxygen gas in the sputtering gas is not particularly limited, but for example, 1 to 10%, preferably 2 to 6% can be mixed with the inert gas.

  The gas pressure at the time of forming the oxide film varies depending on the type of apparatus and the like, and thus cannot be generally specified, but is preferably 1.0 Pa or less, for example, 0.2 to 1.0 Pa. . When the gas pressure at the time of film formation exceeds 1.0 Pa, the oxide film grains become coarse and the film quality is not high, so that the adhesion with the metal film is weakened and the film is peeled off. If the gas pressure during film formation is less than 0.2 Pa, the gas pressure is low, so that argon plasma in the sputtering method becomes unstable, and the film quality of the formed film may deteriorate. Moreover, it is desirable that the resin film substrate temperature during film formation be at least 180 ° C. or higher, particularly 180 to 220 ° C. Thereby, a heat-resistant light-shielding film having a dense oxide film is obtained. A resin film substrate temperature of less than 180 ° C. is not preferable because a dense oxide film cannot be formed. Note that the film thickness of the oxide film is controlled by the film conveyance speed during film formation and the input power to the target.

Thereby, the heat resistant light-shielding film in which the metal film and the oxide film are formed on one surface of the base film can be obtained. In order to obtain a heat-resistant light-shielding film in which a metal film and an oxide film are formed on both sides, the metal film and the oxide film are further supplied to the sputtering apparatus and similarly on the back surface of the resin film substrate by sputtering. Are sequentially formed. That is, the heat-resistant light-shielding film having the metal film (B) and the oxide film (C) formed on one side of the resin film substrate (A) is supplied to a sputtering apparatus in an inverted state, and the resin film base is formed by sputtering. A metal film (B) and an oxide film (C) are sequentially formed on the surface of the material (A).
As described above, as described above, the gas barrier film forming target, the metal film forming target, and the oxide film forming target are used, but the gas barrier film forming target and the metal film forming target, or The gas barrier film forming target and the oxide film forming target can be formed by using the same target and changing the gas atmosphere. It is not necessary to arrange three types of targets in the vacuum chamber, and the vacuum apparatus can be simplified and the cost can be reduced.

  In addition, in order to form the metal film and the oxide film, the film winding type sputtering apparatus is exemplified, and the method of continuously forming the film has been described in detail, but the present invention is not limited to this, A sheet-like resin film substrate, not a roll, can also be produced by a method in which a metal film and an oxide film are formed by stationaryly fixing or passing through a surface facing the target. However, in this case, operations such as switching of the atmospheric gas and loading / stopping of the film are added and become complicated. Further, the base film may be fixed to the apparatus in a state of being cut into a predetermined size, even if it is not a roll.

3. Applications of heat-resistant light-shielding film The heat-resistant light-shielding film of the present invention is a diaphragm of a digital camera, a blade of a shutter device, a diaphragm of a digital video camera, a diaphragm blade of a light amount adjusting device (auto iris), a diaphragm of a liquid crystal projector or a diaphragm of a light amount adjusting device. It can be used as a blade. In particular, it is useful as a diaphragm for projectors requiring heat resistance and a diaphragm blade material for a light quantity adjusting device (auto iris).

In order to use the heat-resistant light-shielding film as a diaphragm blade material for a diaphragm or a light amount adjusting device (auto iris), a punching process that does not cause end face cracks may be performed. The diaphragm may be a single heat-resistant light-shielding plate provided with a hole whose aperture diameter is defined in advance, and this heat-resistant light-shielding plate can be used as a mechanism provided so as to freely enter and exit the projection optical path. In addition, the diaphragm blades of the light quantity adjusting device (auto iris) are used as a plurality of diaphragm blades, which are used as a mechanism capable of adjusting the light quantity by moving the diaphragm blades and changing the aperture diameter of the diaphragm. it can.
FIG. 3 is a schematic diagram showing a diaphragm mechanism of a light quantity adjusting device equipped with a heat-resistant light-shielding blade 12 subjected to punching. The heat-resistant light-shielding blade 12 is provided with a guide hole 13, a guide pin 14 that engages with a drive motor, and a hole 17 that is attached to a substrate 16 provided with a pin 15 that controls the operating position of the light-shielding blade. In addition, although there is an opening 18 through which the lamp light passes in the center of the substrate 16, the light shielding blade may have various shapes depending on the structure of the diaphragm device. Since the heat-resistant light-shielding film of the present invention uses a resin film as a base material, the weight can be reduced, and the drive member that drives the light-shielding blade can be downsized and the power consumption can be reduced.

  Next, the present invention will be specifically described using examples and comparative examples. In addition, evaluation of the obtained heat-resistant light-shielding film was performed by the following method.

(Optical density, reflectance)
Using a spectrophotometer, the light-shielding property and reflectance in the visible light region with a wavelength of 380 nm to 780 nm were measured. The light shielding property was converted by the following equation using the transmittance (T) measured with a spectrophotometer.
Optical density = Log (1 / T)
In the diaphragm blades of the shutter device and the light amount adjusting diaphragm device, it is necessary that the optical density is 4 or more and the maximum reflectance is 5% or less.
(Surface gloss)
The surface glossiness was measured based on JIS Z8741 using a gloss meter. If the surface glossiness is less than 3%, the glossiness is good.
(Coefficient of friction)
The static friction coefficient and the dynamic friction coefficient were measured based on JIS D1894. When the static friction coefficient and the dynamic friction coefficient were 0.3 or less, it was judged as good (◯), and those exceeding 0.3 were judged as insufficient (x).
(Surface roughness)
The arithmetic average height Ra of the obtained heat-resistant light-shielding film was measured with a surface roughness meter.
(Heat-resistant)
The heat resistance characteristics of the obtained heat-resistant light-shielding film were evaluated by the following procedure. The produced heat-resistant light-shielding film was allowed to stand for 24 hours in an oven (Advantech) heated at 220 ° C. and then taken out. The evaluation was good (◯) when there was no warpage or film discoloration, and was insufficient (×) when there was warpage or film discoloration.
(Adhesion)
The adhesion of the film after the heat test was evaluated based on JIS C0021. The evaluation was good (◯) when there was no film peeling, and insufficient (×) when there was film peeling.
(Conductivity)
The surface resistance value of the obtained heat-resistant light-shielding film was measured based on JIS K6911.

Example 1
A light-shielding metal film and a low-reflective oxide film were formed using the winding type sputtering apparatus shown in FIG. First, a target 10 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 cooling can roll 7. A film transport unit configured by the unwinding roll 4, the cooling can roll 7, the winding roll 8, and the like is separated from the magnetron cathode 9 by a partition wall 11. Next, the roll-shaped resin film substrate 1 was set on the unwinding roll 4. The polyimide (PI) film was subjected to surface processing by sand blasting, the arithmetic average height Ra was set to 0.5 μm, and the obtained polyimide (PI) film was heated at a temperature of 200 ° C. or more before sputtering and dried.
Next, after the inside of the vacuum chamber 6 is evacuated by a vacuum pump 5 such as a turbo molecular pump, the film is discharged between the cooling can roll 7 and the cathode, and the resin film substrate 1 is transported in close contact with the surface of the cooling can roll. Went.
First, a Ni—W target was placed on the cathode, and a metal film was formed from this cathode by direct current sputtering. The metal film was formed using a pure argon gas (purity 99.999%) as a sputtering gas. The sputtering gas pressure during film formation was 0.4 to 1.0 Pa. The film thickness of the metal film was controlled by controlling the film conveyance speed and the input power to the target during film formation. The resin film substrate 1 unloaded from the unwinding roll 4 was taken up by the winding roll 8 through the surface of the cooling can roll 7 on the way.
Next, a Ti target was set on the cathode, the roll on which the metal film was formed was set and supplied to the apparatus, and a low-reflection metal oxide film was formed on the metal film from this cathode by DC sputtering. The low-reflective oxide film was formed using argon gas in which 2 to 6% of oxygen gas was mixed with sputtering gas. The sputtering gas pressure during film formation was 0.4 to 1.0 Pa. The film thickness of the oxide film was controlled by controlling the film conveyance speed during film formation and the input power to the target. The film 1 unloaded from the unwinding roll 4 passed through the surface of the cooling can roll 7 and was wound up by the winding roll 8 on the way.
When the surface temperature of the film at the time of sputtering was measured with an infrared radiation thermometer from the observation window of the quartz glass of the winding type sputtering apparatus, the temperature was 180 to 220 ° C. The same result was obtained even when the maximum heating temperature during film formation was checked using a thermolabel (manufactured by Ivy Giken, model number: 101-8-176) that had been attached to the film surface before film formation. It was.
The composition of the obtained metal film was confirmed to be almost the same as the target composition from ICP emission analysis and EPMA quantitative analysis. Moreover, it confirmed that the oxide film of the target metal was obtained as a low reflective oxide film. Moreover, the film thickness of the metal film and the oxide film was measured from cross-sectional TEM observation, and it was confirmed that the film thickness was a predetermined film thickness.
In this way, a 100 nm-thick metal film and a 50 nm-thickness oxide film were sequentially formed on both sides of a 75 μm-thick polyimide (PI) film to produce a heat-resistant light-shielding film. The surface of this polyimide (PI) film is sandblasted at a predetermined discharge time, discharge pressure, and conveyance speed, and fine irregularities with an arithmetic average height of Ra 0.5 μm are formed on both surfaces. Such film formation was performed on each side of the film to produce a light shielding film having a symmetrical structure around a polyimide (PI) film substrate.
Next, the produced heat-resistant light-shielding film was evaluated by the above method. As a result, the optical density was 4 or more, and the maximum reflectance was 1% or less. The glossiness was 2% or less, and the glossiness was good. The static friction coefficient and the dynamic friction coefficient were 0.3 or less, which was favorable. The surface resistance value was 300Ω / □, and the arithmetic average height of the surface was 0.4 μm. The heat-resistant light-shielding film after heating did not warp and did not discolor. Moreover, there was no film peeling and it was favorable. Moreover, when the scratch hardness test (pencil method) was performed based on JIS K5600-5-4, it was H or more of sufficient hardness level. The light-shielding properties, reflection properties, glossiness, and friction coefficient were unchanged from those before heating. The construction and characteristics of the heat-resistant light-shielding film thus produced are summarized in Table 1.
The obtained heat-resistant light-shielding film is good in all of the optical density, reflectance, surface glossiness, heat resistance, friction coefficient, and conductivity. It can be seen that it can be used as a member such as a diaphragm of a liquid crystal projector used in the above.

(Example 2)
A heat-resistant light-shielding film was produced under exactly the same conditions as in Example 1 except that only the thickness of the metal film was changed to 50 nm.
Evaluation (optical characteristics, heat resistance) of the produced heat-resistant light-shielding film was carried out under the same method and conditions as in Example 1. When the surface temperature of the film at the time of sputtering was measured by the same method as in Example 1, the temperature was 180 to 220 ° C., which was the same film temperature as in Example 1.
As a result, the same optical density, reflectance, and glossiness as those of Example 1 were obtained. Further, it was confirmed that the surface resistance value was 300Ω / □, and the arithmetic average height Ra of the surface was 0.4 μm. Moreover, even in the adhesion evaluation of the film after the heating test at 220 ° C. for 24 hours, it was found that the film had heat resistance characteristics equivalent to those of Example 1 without warping or film peeling. The construction and characteristics of the heat-resistant light-shielding film thus produced are summarized in Table 1.
Therefore, such a heat-resistant light-shielding film can be used as a member such as a diaphragm of a liquid crystal projector used in a high heat environment of about 200 ° C.

(Example 3)
A heat-resistant light-shielding film was produced under exactly the same conditions as in Example 1 except that only the thickness of the metal film was changed to 150 nm.
Evaluation (optical characteristics, heat resistance) of the produced heat-resistant light-shielding film was carried out under the same method and conditions as in Example 1. When the surface temperature of the film at the time of sputtering was measured by the same method as in Example 1, the temperature was 180 to 220 ° C., which was the same film temperature as in Example 1.
As a result, the same optical density, reflectance, and glossiness as those of Example 1 were obtained. Further, it was confirmed that the surface resistance value was 200Ω / □, and the arithmetic average height Ra of the surface was 0.3 μm. Moreover, even in the adhesion evaluation of the film after the heating test at 220 ° C. for 24 hours, it was found that the film had heat resistance characteristics equivalent to those of Example 1 without warping or film peeling. The construction and characteristics of the heat-resistant light-shielding film thus produced are summarized in Table 1.
Therefore, such a heat-resistant light-shielding film can be used as a member such as a diaphragm of a liquid crystal projector used in a high heat environment of about 200 ° C.

Example 4
A light-shielding film was produced by changing only the surface processing conditions of the polyimide film by sandblasting. That is, a heat-resistant light-shielding film having the same film configuration was produced under the same conditions as in Example 1 except that a polyimide film having an arithmetic average height Ra of 0.2 μm was used. However, the kind and thickness of polyimide are the same as those in Example 1.
When the surface temperature of the film at the time of sputtering was measured by the same method as in Example 1, the temperature was 180 to 220 ° C., which was the same film temperature as in Example 1. Evaluation (optical characteristics, heat resistance) of the produced heat-resistant light-shielding film was carried out under the same method and conditions as in Example 1.
As a result, the same optical density, reflectance, and glossiness as those of Example 1 were obtained. Further, it was confirmed that the surface resistance value was 300Ω / □, and the arithmetic average height Ra of the surface was 0.1 μm. Moreover, even in the adhesion evaluation of the film after the heating test at 220 ° C. for 24 hours, it was found that the film had heat resistance characteristics equivalent to those of Example 1 without warping or film peeling. The construction and characteristics of the heat-resistant light-shielding film thus produced are summarized in Table 1.
Therefore, such a heat-resistant light-shielding film can be used as a member such as a diaphragm of a liquid crystal projector used in a high heat environment of about 200 ° C.

(Example 5)
A heat-resistant light-shielding film was produced under exactly the same conditions as in Example 1 except that a polyimide film having an arithmetic average height Ra of 0.8 μm, which was produced by changing the surface processing conditions by sandblasting, was used. However, the kind and thickness of polyimide are the same as those in Example 1.
When the surface temperature of the film at the time of sputtering was measured by the same method as in Example 1, the temperature was 180 to 220 ° C., which was the same film temperature as in Example 1.
Evaluation (optical characteristics, heat resistance) of the produced heat-resistant light-shielding film was carried out under the same method and conditions as in Example 1. As a result, the same optical density, reflectance, and glossiness as those of Example 1 were obtained. Further, it was confirmed that the surface resistance value was 300Ω / □, and the arithmetic average height Ra of the surface was 0.7 μm. Moreover, even in the adhesion evaluation of the film after the heating test at 220 ° C. for 24 hours, it was found that the film had heat resistance characteristics equivalent to those of Example 1 without warping or film peeling. The construction and characteristics of the heat-resistant light-shielding film thus produced are summarized in Table 1.
Therefore, such a heat-resistant light-shielding film can be used as a member such as a diaphragm of a liquid crystal projector used in a high heat environment of about 200 ° C.

(Example 6)
A heat-resistant light-shielding film was produced under exactly the same conditions as in Example 1 except that the metal light-shielding film and the low-reflection metal oxide film were formed by sandblasting only on one side, not both sides of the film.
When the surface temperature of the film at the time of sputtering was measured by the same method as in Example 1, the temperature was 180 to 220 ° C., which was the same film temperature as in Example 1.
Evaluation (optical characteristics, heat resistance) of the produced heat-resistant light-shielding film was carried out under the same method and conditions as in Example 1. As a result, the same optical density, reflectance, and glossiness as those of Example 1 were obtained. Further, it was confirmed that the surface resistance value was 300Ω / □, and the arithmetic average height Ra of the surface was 0.4 μm. Moreover, although the adhesive evaluation of the film | membrane after a 24-hour heating test was performed at 220 degreeC, it turned out that there is no film | membrane peeling and it has the heat resistance characteristic equivalent to Example 1. FIG. The warp was slightly caused by the heating test, and a warp of 2 mm at the maximum occurred when a sample processed into a 5 cm square was placed on a flat surface. This is the effect of film stress caused by film formation on only one side, but if this degree of warping, it can be used by adhering and fixing multiple places to the support substrate when used as a diaphragm. it can. The construction and characteristics of the heat-resistant light-shielding film thus produced are summarized in Table 1.
Therefore, such a light shielding film can be used as a member such as a diaphragm of a liquid crystal projector used in a high heat environment of about 200 ° C.
In addition, this heat-resistant light-shielding film can be applied to the wall surface of optical members that require low reflectivity and low glossiness, such as a lens barrel, if an adhesive is applied to the non-film-forming surface side. A glossy surface can be formed.

(Example 7)
When producing a metal film, using a Ni-Ti target, when producing a low reflective oxide film, using a Ti target, a light-shielding nickel titanium film in the same manner as in Example 1. A low heat-resistant titanium oxide film was formed on both sides to make a heat-resistant light-shielding film. The type of film and the matting conditions of the film are the same as in Example 1. The film thickness is shown in Table 1.
When the surface temperature of the film at the time of sputtering was measured by the same method as in Example 1, the temperature was 180 to 220 ° C., which was the same film temperature as in Example 1.
When the obtained light shielding film was evaluated by the same method as in Example 1, it was found that a light shielding film having an optical density of 4 or more, a maximum reflectance of 4% at a wavelength of 380 to 780 nm, and a glossiness of 3% or less was obtained. It was. The heat resistance was also evaluated in the same manner, but the results were exactly the same as in Example 1. Further, it was confirmed that the surface resistance value was 400Ω / □ or less, and the arithmetic average height Ra of the surface was 0.4 μm.
Therefore, such a heat-resistant light-shielding film can be used as a member such as a diaphragm of a liquid crystal projector used in a high heat environment of about 200 ° C.

(Example 8)
A heat-resistant light-shielding film was prototyped in the same manner as in Example 7 except that the thickness of the metal oxide film was changed to 20 nm.
When the surface temperature of the film at the time of sputtering was measured by the same method as in Example 1, the temperature was 180 to 220 ° C., which was the same film temperature as in Example 1.
When the obtained light shielding film was evaluated by the same method as in Example 1, it was found that a light shielding film having an optical density of 4 or more, a maximum reflectance of 5% at a wavelength of 380 to 780 nm, and a glossiness of 3% or less was obtained. It was. The heat resistance was also evaluated in the same manner, but the results were exactly the same as in Example 1. Further, it was confirmed that the surface resistance value was 400Ω / □ or less, and the arithmetic average height Ra of the surface was 0.4 μm.
Therefore, such a heat-resistant light-shielding film can be used as a member such as a diaphragm of a liquid crystal projector used in a high heat environment of about 200 ° C.

Example 9
A heat-resistant light-shielding film was prototyped in the same manner as in Example 7 except that the thickness of the metal oxide film was changed to 140 nm.
When the surface temperature of the film at the time of sputtering was measured by the same method as in Example 1, the temperature was 180 to 220 ° C., which was the same film temperature as in Example 1.
When the obtained light shielding film was evaluated by the same method as in Example 1, it was found that a light shielding film having an optical density of 4 or more, a maximum reflectance of 5% at a wavelength of 380 to 780 nm, and a glossiness of 3% or less was obtained. It was. The heat resistance was also evaluated in the same manner, but the results were exactly the same as in Example 1. Further, it was confirmed that the surface resistance value was 400Ω / □ or less, and the arithmetic average height Ra of the surface was 0.4 μm.
Therefore, such a heat-resistant light-shielding film can be used as a member such as a diaphragm of a liquid crystal projector used in a high heat environment of about 200 ° C.

(Example 10)
When producing a light-shielding metal film, Ni—Ta is used, and when producing a low-reflective oxide film, a Ti target is used in the same manner as in Example 1 to produce a light-shielding nickel film. A tantalum film and a low-reflective titanium oxide film were formed on both sides to produce a heat-resistant light-shielding film. The type of film and the matting conditions of the film are the same as in Example 1. The film thickness is shown in Table 1.
When the surface temperature of the film at the time of sputtering was measured by the same method as in Example 1, the temperature was 180 to 220 ° C., which was the same film temperature as in Example 1.
Evaluation (optical characteristics, heat resistance) of the produced heat-resistant light-shielding film was carried out under the same method and conditions as in Example 1. As a result, it was found that a light-shielding film having an optical density of 4 or more, a maximum reflectance of 2% at a wavelength of 380 to 780 nm, and a glossiness of 2% or less was obtained. Further, in the case of the same conditions as in Example 1, it was confirmed that the surface resistance value was 800Ω / □, and the arithmetic average height Ra of the surface was 0.3 μm. Moreover, although the adhesiveness of the film was evaluated after a heating test at 220 ° C. for 24 hours, it was found that there was no warpage or film peeling and the heat resistance was equivalent to that of Example 1.
Therefore, such a heat-resistant light-shielding film can be used as a member such as a diaphragm of a liquid crystal projector used in a high heat environment of about 200 ° C.

(Example 11)
A heat-resistant light-shielding film was prototyped in the same manner as in Example 10 except that the thickness of the metal oxide film was changed to 20 nm.
When the surface temperature of the film at the time of sputtering was measured by the same method as in Example 1, the temperature was 180 to 220 ° C., which was the same film temperature as in Example 1.
Evaluation (optical characteristics, heat resistance) of the produced heat-resistant light-shielding film was carried out under the same method and conditions as in Example 1. As a result, it was found that a light-shielding film having an optical density of 4 or more, a maximum reflectance of 2% at a wavelength of 380 to 780 nm, and a glossiness of 2% or less was obtained. Further, in the case of the same conditions as in Example 1, it was confirmed that the surface resistance value was 800Ω / □, and the arithmetic average height Ra of the surface was 0.3 μm. Moreover, although the adhesiveness of the film was evaluated after a heating test at 220 ° C. for 24 hours, it was found that there was no warpage or film peeling and the heat resistance was equivalent to that of Example 1.
Therefore, such a heat-resistant light-shielding film can be used as a member such as a diaphragm of a liquid crystal projector used in a high heat environment of about 200 ° C.

(Example 12)
A heat-resistant light-shielding film was prototyped in the same manner as in Example 10 except that the thickness of the metal oxide film was changed to 140 nm.
When the surface temperature of the film at the time of sputtering was measured by the same method as in Example 1, the temperature was 180 to 220 ° C., which was the same film temperature as in Example 1.
Evaluation (optical characteristics, heat resistance) of the produced heat-resistant light-shielding film was carried out under the same method and conditions as in Example 1. As a result, it was found that a light-shielding film having an optical density of 4 or more, a maximum reflectance of 2% at a wavelength of 380 to 780 nm, and a glossiness of 2% or less was obtained. Further, in the case of the same conditions as in Example 1, it was confirmed that the surface resistance value was 1 × 10 ³ Ω / □, and the arithmetic average height Ra of the surface was 0.3 μm. Moreover, although the adhesiveness of the film was evaluated after a heating test at 220 ° C. for 24 hours, it was found that there was no warpage or film peeling and the heat resistance was equivalent to that of Example 1.
Therefore, such a heat-resistant light-shielding film can be used as a member such as a diaphragm of a liquid crystal projector used in a high heat environment of about 200 ° C.

(Example 13)
When producing a metal film, using a Ni-Mo target, when producing a low-reflective oxide film, using a Ti target, a light-shielding nickel-molybdenum film in the same manner as in Example 1. A low heat-resistant titanium oxide film was formed on both sides to make a heat-resistant light-shielding film. The type of film and the matting conditions of the film are the same as in Example 1.
When the surface temperature of the film at the time of sputtering was measured by the same method as in Example 1, the temperature was 180 to 220 ° C., which was the same film temperature as in Example 1.
When the obtained light shielding film was evaluated by the same method as in Example 1, it was found that a light shielding film having an optical density of 4 or more, a maximum reflectance of 4% at a wavelength of 380 to 780 nm, and a glossiness of 3% or less was obtained. It was. The heat resistance was also evaluated in the same manner, but the results were exactly the same as in Example 1. Further, it was confirmed that the surface resistance value was 300Ω / □ or less, and the arithmetic average height Ra of the surface was 0.4 μm.
Therefore, such a heat-resistant light-shielding film can be used as a member such as a diaphragm of a liquid crystal projector used in a high heat environment of about 200 ° C.

(Example 14)
A heat-resistant light-shielding film was prototyped in the same manner as in Example 13 except that the thickness of the metal oxide film was changed to 20 nm.
When the surface temperature of the film at the time of sputtering was measured by the same method as in Example 1, the temperature was 180 to 220 ° C., which was the same film temperature as in Example 1.
When the obtained light shielding film was evaluated by the same method as in Example 1, it was found that a light shielding film having an optical density of 4 or more, a maximum reflectance of 4% at a wavelength of 380 to 780 nm, and a glossiness of 3% or less was obtained. It was. The heat resistance was also evaluated in the same manner, but the results were exactly the same as in Example 1. Further, it was confirmed that the surface resistance value was 200Ω / □ or less, and the arithmetic average height Ra of the surface was 0.4 μm.
Therefore, such a heat-resistant light-shielding film can be used as a member such as a diaphragm of a liquid crystal projector used in a high heat environment of about 200 ° C.

(Example 15)
A heat-resistant light-shielding film was prototyped in the same manner as in Example 13 except that the thickness of the metal oxide film was changed to 140 nm.
When the surface temperature of the film at the time of sputtering was measured by the same method as in Example 1, the temperature was 180 to 220 ° C., which was the same film temperature as in Example 1.
When the obtained light shielding film was evaluated by the same method as in Example 1, it was found that a light shielding film having an optical density of 4 or more, a maximum reflectance of 4% at a wavelength of 380 to 780 nm, and a glossiness of 3% or less was obtained. It was. The heat resistance was also evaluated in the same manner, but the results were exactly the same as in Example 1. Further, it was confirmed that the surface resistance value was 500Ω / □ or less, and the arithmetic average height Ra of the surface was 0.4 μm.
Therefore, such a heat-resistant light-shielding film can be used as a member such as a diaphragm of a liquid crystal projector used in a high heat environment of about 200 ° C.

(Example 16)
When producing a light-shielding metal film, a Ni-Nb target is used, and when producing a low-reflective oxide film, a Ti target is used in the same manner as in Example 1 to produce a light-shielding metal film. A nickel niobium film and a low-reflective titanium oxide film were formed on both sides to produce a heat-resistant light-shielding film. The type of film and the matting conditions of the film are the same as in Example 1. The film thickness is shown in Table 1.
When the surface temperature of the film at the time of sputtering was measured by the same method as in Example 1, the temperature was 180 to 220 ° C., which was the same film temperature as in Example 1.
Evaluation (optical characteristics, heat resistance) of the produced heat-resistant light-shielding film was carried out under the same method and conditions as in Example 1. As a result, it was found that a light-shielding film having an optical density of 4 or more, a maximum reflectance of 1% at a wavelength of 380 to 780 nm, and a glossiness of 2% or less was obtained. Further, in the case of the same conditions as in Example 1, it was confirmed that the surface resistance value was 800Ω / □, and the arithmetic average height Ra of the surface was 0.3 μm. Moreover, although the adhesiveness of the film was evaluated after a heating test at 220 ° C. for 24 hours, it was found that there was no warpage or film peeling and the heat resistance was equivalent to that of Example 1.
Therefore, such a heat-resistant light-shielding film can be used as a member such as a diaphragm of a liquid crystal projector used in a high heat environment of about 200 ° C.

(Example 17)
A heat-resistant light-shielding film was prototyped in the same manner as in Example 16 except that the thickness of the metal oxide film was changed to 20 nm.
When the surface temperature of the film at the time of sputtering was measured by the same method as in Example 1, the temperature was 180 to 220 ° C., which was the same film temperature as in Example 1.
Evaluation (optical characteristics, heat resistance) of the produced heat-resistant light-shielding film was carried out under the same method and conditions as in Example 1. As a result, it was found that a light-shielding film having an optical density of 4 or more, a maximum reflectance of 1% at a wavelength of 380 to 780 nm, and a glossiness of 2% or less was obtained. Moreover, in the case of the same conditions as Example 1, it was confirmed that the surface resistance value was 700Ω / □ and the arithmetic average height Ra of the surface was 0.3 μm. Moreover, although the adhesiveness of the film was evaluated after a heating test at 220 ° C. for 24 hours, it was found that there was no warpage or film peeling and the heat resistance was equivalent to that of Example 1.
Therefore, such a heat-resistant light-shielding film can be used as a member such as a diaphragm of a liquid crystal projector used in a high heat environment of about 200 ° C.

(Example 18)
A heat-resistant light-shielding film was prototyped in the same manner as in Example 16 except that the thickness of the metal oxide film was changed to 140 nm.
When the surface temperature of the film at the time of sputtering was measured by the same method as in Example 1, the temperature was 180 to 220 ° C., which was the same film temperature as in Example 1.
Evaluation (optical characteristics, heat resistance) of the produced heat-resistant light-shielding film was carried out under the same method and conditions as in Example 1. As a result, it was found that a light-shielding film having an optical density of 4 or more, a maximum reflectance of 1% at a wavelength of 380 to 780 nm, and a glossiness of 2% or less was obtained. Further, in the case of the same conditions as in Example 1, it was confirmed that the surface resistance value was 1 × 10 ³ Ω / □, and the arithmetic average height Ra of the surface was 0.3 μm. Moreover, although the adhesiveness of the film was evaluated after a heating test at 220 ° C. for 24 hours, it was found that there was no warpage or film peeling and the heat resistance was equivalent to that of Example 1.
Therefore, such a heat-resistant light-shielding film can be used as a member such as a diaphragm of a liquid crystal projector used in a high heat environment of about 200 ° C.

(Example 19)
A light-shielding nickel-molybdenum film in the same manner as in Example 1 using a Ti target when forming a low-reflective oxide film using a Ni-Co target when forming a metal film. A low heat-resistant titanium oxide film was formed on both sides to make a heat-resistant light-shielding film. The type of film and the matting conditions of the film are the same as in Example 1. The film thickness is shown in Table 1.
When the surface temperature of the film at the time of sputtering was measured by the same method as in Example 1, the temperature was 180 to 220 ° C., which was the same film temperature as in Example 1.
When the obtained light shielding film was evaluated in the same manner as in Example 1, it was found that a light shielding film having an optical density of 4 or more, a maximum reflectance of 3% at a wavelength of 380 to 780 nm, and a glossiness of 3% or less was obtained. It was. The heat resistance was also evaluated in the same manner, but the results were exactly the same as in Example 1. Further, it was confirmed that the surface resistance value was 200Ω / □ or less, and the arithmetic average height Ra of the surface was 0.3 μm.
Therefore, such a heat-resistant light-shielding film can be used as a member such as a diaphragm of a liquid crystal projector used in a high heat environment of about 200 ° C.

(Example 20)
A heat-resistant light-shielding film was prototyped in the same manner as in Example 19 except that the thickness of the metal oxide film was changed to 20 nm.
When the surface temperature of the film at the time of sputtering was measured by the same method as in Example 1, the temperature was 180 to 220 ° C., which was the same film temperature as in Example 1.
When the obtained light shielding film was evaluated in the same manner as in Example 1, it was found that a light shielding film having an optical density of 4 or more, a maximum reflectance of 3% at a wavelength of 380 to 780 nm, and a glossiness of 3% or less was obtained. It was. The heat resistance was also evaluated in the same manner, but the results were exactly the same as in Example 1. Further, it was confirmed that the surface resistance value was 200Ω / □ or less, and the arithmetic average height Ra of the surface was 0.3 μm.
Therefore, such a heat-resistant light-shielding film can be used as a member such as a diaphragm of a liquid crystal projector used in a high heat environment of about 200 ° C.

(Example 21)
A heat-resistant light-shielding film was prototyped in the same manner as in Example 19 except that the thickness of the metal oxide film was changed to 140 nm.
When the surface temperature of the film at the time of sputtering was measured by the same method as in Example 1, the temperature was 180 to 220 ° C., which was the same film temperature as in Example 1.
When the obtained light shielding film was evaluated in the same manner as in Example 1, it was found that a light shielding film having an optical density of 4 or more, a maximum reflectance of 3% at a wavelength of 380 to 780 nm, and a glossiness of 3% or less was obtained. It was. The heat resistance was also evaluated in the same manner, but the results were exactly the same as in Example 1. Further, it was confirmed that the surface resistance value was 300Ω / □ or less, and the arithmetic average height Ra of the surface was 0.3 μm.
Therefore, such a heat-resistant light-shielding film can be used as a member such as a diaphragm of a liquid crystal projector used in a high heat environment of about 200 ° C.

(Example 22)
When producing a metal film, a Ni-Fe target is used, and when producing a low-reflective oxide film, a Ti target is used in the same manner as in Example 1, using a light-shielding Ni-Fe target. A heat-resistant light-shielding film was fabricated by forming a film and a low-reflective titanium oxide film on both sides. The type of film and the matting conditions of the film are the same as in Example 1. The film thickness is shown in Table 1.
When the surface temperature of the film at the time of sputtering was measured by the same method as in Example 1, the temperature was 180 to 220 ° C., which was the same film temperature as in Example 1.
When the obtained light shielding film was evaluated in the same manner as in Example 1, it was found that a light shielding film having an optical density of 4 or more, a maximum reflectance of 3% at a wavelength of 380 to 780 nm, and a glossiness of 3% or less was obtained. It was. The heat resistance was also evaluated in the same manner, but the results were exactly the same as in Example 1. Further, it was confirmed that the surface resistance value was 200Ω / □ or less, and the arithmetic average height Ra of the surface was 0.4 μm.
Therefore, such a heat-resistant light-shielding film can be used as a member such as a diaphragm of a liquid crystal projector used in a high heat environment of about 200 ° C.

(Example 23)
A heat-resistant light-shielding film was prototyped in the same manner as in Example 22 except that the thickness of the metal oxide film was changed to 20 nm.
When the surface temperature of the film at the time of sputtering was measured by the same method as in Example 1, the temperature was 180 to 220 ° C., which was the same film temperature as in Example 1.
When the obtained light shielding film was evaluated in the same manner as in Example 1, it was found that a light shielding film having an optical density of 4 or more, a maximum reflectance of 3% at a wavelength of 380 to 780 nm, and a glossiness of 3% or less was obtained. It was. The heat resistance was also evaluated in the same manner, but the results were exactly the same as in Example 1. Further, it was confirmed that the surface resistance value was 200Ω / □ or less, and the arithmetic average height Ra of the surface was 0.4 μm.
Therefore, such a heat-resistant light-shielding film can be used as a member such as a diaphragm of a liquid crystal projector used in a high heat environment of about 200 ° C.

(Example 24)
A heat-resistant light-shielding film was prototyped in the same manner as in Example 22 except that the thickness of the metal oxide film was changed to 140 nm.
When the surface temperature of the film at the time of sputtering was measured by the same method as in Example 1, the temperature was 180 to 220 ° C., which was the same film temperature as in Example 1.
When the obtained light shielding film was evaluated in the same manner as in Example 1, it was found that a light shielding film having an optical density of 4 or more, a maximum reflectance of 3% at a wavelength of 380 to 780 nm, and a glossiness of 3% or less was obtained. It was. The heat resistance was also evaluated in the same manner, but the results were exactly the same as in Example 1. Further, it was confirmed that the surface resistance value was 300Ω / □ or less, and the arithmetic average height Ra of the surface was 0.4 μm.
Therefore, such a heat-resistant light-shielding film can be used as a member such as a diaphragm of a liquid crystal projector used in a high heat environment of about 200 ° C.

(Example 25)
When producing a metal film, a pure Ni target is used, and when producing a low-reflective oxide film, a Ti target is used to produce a light-shielding Ni film and a low-reflection film in the same manner as in Example 1. A reflective heat-resistant light-shielding film was fabricated on both sides with a reflective titanium oxide film. The type of film and the matting conditions of the film are the same as in Example 1. The film thickness is shown in Table 1.
When the surface temperature of the film at the time of sputtering was measured by the same method as in Example 1, the temperature was 180 to 220 ° C., which was the same film temperature as in Example 1.
As a result, when the obtained light shielding film was evaluated by the same method as in Example 1, a light shielding film having an optical density of 4 or more, a maximum reflectance of 2% at a wavelength of 380 to 780 nm, and a glossiness of 2% or less was obtained. I understood it. Further, it was confirmed that the surface resistance value was 500Ω / □, and the arithmetic average height Ra of the surface was 0.4 μm. As for heat resistance, slight film peeling was observed. When the peeled part was observed with the scanning electron microscope, it turned out that it peeled in the interface of a metal film and a polyimide film. Therefore, although such a heat-resistant light-shielding film can be used for many optical system applications, it has been found that the heat-resistant light-shielding film is not suitable as a member such as a diaphragm of a liquid crystal projector used in a high heat environment of about 200 ° C.

(Example 26)
When producing a metal film, using a Ni-W target, and when producing a low-reflective oxide film, using a W target, the light-shielding Ni-W in the same manner as in Example 1. A heat-resistant light-shielding film was fabricated by forming a film and a low-reflective tungsten oxide film on both sides.
When the surface temperature of the film at the time of sputtering was measured by the same method as in Example 1, the temperature was 180 to 220 ° C., which was the same film temperature as in Example 1.
As a result, when the obtained light shielding film was evaluated by the same method as in Example 1, a light shielding film having an optical density of 4 or more, a maximum reflectance of 2% at a wavelength of 380 to 780 nm, and a glossiness of 2% or less was obtained. I understood it. The heat resistance was also evaluated in the same manner, but the results were exactly the same as in Example 1. Further, it was confirmed that the surface resistance value was 400Ω / □, and the arithmetic average height Ra of the surface was 0.4 μm.
Therefore, such a heat-resistant light-shielding film can be used as a member such as a diaphragm of a liquid crystal projector used in a high heat environment of about 200 ° C.

(Example 27)
A heat-resistant light-shielding film was prototyped in the same manner as in Example 26 except that the Ta target was used when the low reflective oxide film was produced.
When the surface temperature of the film at the time of sputtering was measured by the same method as in Example 1, the temperature was 180 to 220 ° C., which was the same film temperature as in Example 1.
As a result, when the obtained light shielding film was evaluated by the same method as in Example 1, a light shielding film having an optical density of 4 or more, a maximum reflectance of 2% at a wavelength of 380 to 780 nm, and a glossiness of 2% or less was obtained. I understood it. The heat resistance was also evaluated in the same manner, but the results were exactly the same as in Example 1. Further, it was confirmed that the surface resistance value was 700Ω / □, and the arithmetic average height Ra of the surface was 0.4 μm.
Therefore, such a heat-resistant light-shielding film can be used as a member such as a diaphragm of a liquid crystal projector used in a high heat environment of about 200 ° C.

(Example 28)
A heat-resistant light-shielding film was prototyped in the same manner as in Example 26, except that the V-target was used when producing the low-reflective oxide film. When the surface temperature of the film at the time of sputtering was measured by the same method as Example 1, it was 180-200 degreeC.
Evaluation (optical characteristics, heat resistance) of the produced heat-resistant light-shielding film was carried out under the same method and conditions as in Example 1. As a result, the same optical density, reflectance, and glossiness as those of Example 1 were obtained. Further, it was confirmed that the surface resistance value was 6 × 10 ³ Ω / □, and the arithmetic average height Ra of the surface was 0.4 μm.
Therefore, such a heat-resistant light-shielding film can be used as a member such as a diaphragm of a liquid crystal projector used in a high heat environment of about 200 ° C.

(Example 29)
A heat-resistant light-shielding film was prototyped in the same manner as in Example 26 except that the Mo target was used when the low reflective oxide film was produced.
When the surface temperature of the film at the time of sputtering was measured by the same method as in Example 1, the temperature was 180 to 220 ° C., which was the same film temperature as in Example 1.
Evaluation (optical characteristics, heat resistance) of the produced heat-resistant light-shielding film was carried out under the same method and conditions as in Example 1. As a result, the same characteristics as in Example 1 were obtained, such as reflectance and glossiness. The optical density was 2, which transmitted light slightly, but it was confirmed that there was no practical problem. Further, it was confirmed that the surface resistance value was 100Ω / □, and the arithmetic average height Ra of the surface was 0.3 μm. Even in the adhesion evaluation of the film after the heating test at 220 ° C. for 24 hours, it was found that there was no warpage or peeling of the film, and the film had heat resistance characteristics equivalent to Example 1. The construction and characteristics of the heat-resistant light-shielding film thus produced are summarized in Table 1.
Therefore, such a heat-resistant light-shielding film can be used as a member such as a diaphragm of a liquid crystal projector used in a high heat environment of about 200 ° C.

(Example 30)
A heat-resistant light-shielding film was prototyped in the same manner as in Example 26, except that the Co target was used when the low reflective oxide film was produced.
When the surface temperature of the film at the time of sputtering was measured by the same method as Example 1, it was 180-220 degreeC.
As a result of evaluation under the same method and conditions as in Example 1, the same characteristics as in Example 1 were obtained, such as optical density, reflectance, glossiness, and heat resistance. Further, it was confirmed that the surface resistance value was 100Ω / □, and the arithmetic average height Ra of the surface was 0.4 μm. Even in the adhesion evaluation of the film after the heating test at 220 ° C. for 24 hours, it was found that there was no warpage or peeling of the film, and the film had heat resistance characteristics equivalent to Example 1. The construction and characteristics of the heat-resistant light-shielding film thus produced are summarized in Table 1.
Therefore, such a heat-resistant light-shielding film can be used as a member such as a diaphragm of a liquid crystal projector used in a high heat environment of about 200 ° C.

(Example 31)
A heat-resistant light-shielding film was prototyped in the same manner as in Example 26, except that the Nb target was changed to the production of the low-reflective oxide film. The type of film and the matting conditions of the film are the same as in Example 1.
When the surface temperature of the film at the time of sputtering was measured by the same method as in Example 1, the temperature was 180 to 220 ° C., which was the same film temperature as in Example 1.
When the obtained light shielding film was evaluated by the same method as in Example 1, it was found that a light shielding film having an optical density of 4 or more, a maximum reflectance of 1% at a wavelength of 380 to 780 nm, and a glossiness of 2% or less was obtained. It was. The heat resistance was also evaluated in the same manner, but the results were exactly the same as in Example 1. Further, it was confirmed that the surface resistance value was 400Ω / □, and the arithmetic average height Ra of the surface was 0.4 μm.
Therefore, such a heat-resistant light-shielding film can be used as a member such as a diaphragm of a liquid crystal projector used in a high heat environment of about 200 ° C.

(Example 32)
A heat-resistant light-shielding film was prototyped in the same manner as in Example 26 except that the Fe-based target was changed to the production of the low-reflective oxide film. The type of film and the matting conditions of the film are the same as in Example 1. When the surface temperature of the film at the time of sputtering was measured by the same method as in Example 1, the temperature was 180 to 220 ° C., which was the same film temperature as in Example 1.
When the obtained light shielding film was evaluated by the same method as in Example 1, it was found that a light shielding film having an optical density of 4 or more, a maximum reflectance of 5% at a wavelength of 380 to 780 nm, and a glossiness of 3% or less was obtained. It was. The heat resistance was also evaluated in the same manner, but the results were exactly the same as in Example 1. Further, it was confirmed that the surface resistance value was 900Ω / □, and the arithmetic average height Ra of the surface was 0.4 μm.
Therefore, such a heat-resistant light-shielding film can be used as a member such as a diaphragm of a liquid crystal projector used in a high heat environment of about 200 ° C.

(Example 33)
A heat-resistant light-shielding film was prototyped in the same manner as in Example 26, except that the Al target was used instead of the low-reflective oxide film. When the surface temperature of the film at the time of sputtering is measured by the same method as in Example 1 in which the kind of film and the matting condition of the film are the same as in Example 1, a film temperature equivalent to that of Example 1 is obtained. It was temperature.
When the obtained light shielding film was evaluated by the same method as in Example 1, it was found that a light shielding film having an optical density of 4 or more, a maximum reflectance of 5% at a wavelength of 380 to 780 nm, and a glossiness of 3% or less was obtained. It was. The heat resistance was also evaluated in the same manner, but the results were exactly the same as in Example 1. Further, it was confirmed that the surface resistance value was 3 × 10 ³ Ω / □, and the arithmetic average height Ra of the surface was 0.4 μm.
Therefore, such a heat-resistant light-shielding film can be used as a member such as a diaphragm of a liquid crystal projector used in a high heat environment of about 200 ° C.

(Example 34)
A heat-resistant light-shielding film was prototyped in the same manner as in Example 26, except that the Si-C target was changed when the low reflective oxide film was produced. The silicon oxycarbide film (Si—C—O film) was formed by reactive sputtering in which oxygen gas was introduced into the sputtering gas. The type of film and the matting conditions of the film are the same as in Example 1.
When the surface temperature of the film at the time of sputtering was measured by the same method as in Example 1, the temperature was 180 to 220 ° C., which was the same film temperature as in Example 1.
When the obtained light shielding film was evaluated by the same method as in Example 1, it was found that a light shielding film having an optical density of 4 or more, a maximum reflectance of 5% at a wavelength of 380 to 780 nm, and a glossiness of 3% or less was obtained. It was. The heat resistance was also evaluated in the same manner, but the results were exactly the same as in Example 1. Further, it was confirmed that the surface resistance value was 1 × 10 ³ Ω / □, and the arithmetic average height Ra of the surface was 0.4 μm.
Therefore, such a heat-resistant light-shielding film can be used as a member such as a diaphragm of a liquid crystal projector used in a high heat environment of about 200 ° C.

(Example 35)
A heat-resistant light-shielding film was prototyped in the same manner as in Example 26 except that the low-reflective oxide film was changed to a 3% Ga-added ZnO target. The type of film and the matting conditions of the film are the same as in Example 1. When the surface temperature of the film at the time of sputtering was measured by the same method as in Example 1, the temperature was 180 to 220 ° C., which was the same film temperature as in Example 1.
When the obtained light shielding film was evaluated by the same method as in Example 1, it was found that a light shielding film having an optical density of 4 or more, a maximum reflectance of 4% at a wavelength of 380 to 780 nm, and a glossiness of 3% or less was obtained. It was. The heat resistance was also evaluated in the same manner, but the results were exactly the same as in Example 1. Further, it was confirmed that the surface resistance value was 10Ω / □, and the arithmetic average height Ra of the surface was 0.4 μm.
Therefore, such a heat-resistant light-shielding film can be used as a member such as a diaphragm of a liquid crystal projector used in a high heat environment of about 200 ° C.

(Example 36)
Except for changing to a titanium carbide target when producing a low-reflective oxide film, a titanium oxide film containing 50 nm-low-reflective carbon (titanium oxide carbide film, The (Ti—C—O film) was prepared by reactive sputtering in which oxygen gas was introduced into the sputtering gas by high-frequency sputtering. When the surface temperature of the film at the time of sputtering was measured by the same method as in Example 1, the temperature was 180 to 220 ° C., which was the same film temperature as in Example 1.
Quantitative analysis was performed with EPMA, and it was confirmed that a titanium oxide carbide film was obtained. When the obtained light shielding film was evaluated by the same method as in Example 1, it was found that a light shielding film having an optical density of 4 or more, a maximum reflectance of 4% at a wavelength of 380 to 780 nm, and a glossiness of 3% or less was obtained. It was. The heat resistance was also evaluated in the same manner, but the results were exactly the same as in Example 1. Further, it was confirmed that the surface resistance value was 4 × 10 ³ Ω / □, and the arithmetic average height Ra of the surface was 0.4 μm.
Therefore, such a heat-resistant light-shielding film can be used as a member such as a diaphragm of a liquid crystal projector used in a high heat environment of about 200 ° C.

(Example 37)
A heat-resistant light-shielding film was produced in the same manner as in Example 26, except that the ITO target (indium oxide target with 10 wt% tin oxide added) was changed when the low reflective oxide film was produced. The ITO film was formed by DC sputtering, and the ITO film used a mixed gas of argon and oxygen as a sputtering gas. A film having a thickness of 75 μm was used.
When the surface temperature of the film at the time of sputtering was measured by the same method as in Example 1, the temperature was 180 to 220 ° C., which was the same film temperature as in Example 1.
When the obtained light shielding film was evaluated by the same method as in Example 1, it was found that a light shielding film having an optical density of 4 or more, a maximum reflectance of 4% at a wavelength of 380 to 780 nm, and a glossiness of 3% or less was obtained. It was. The heat resistance was also evaluated in the same manner, but the results were exactly the same as in Example 1. Further, it was confirmed that the surface resistance value was 20Ω / □, and the arithmetic average height Ra of the surface was 0.4 μm.
Therefore, such a heat-resistant light-shielding film can be used as a member such as a diaphragm of a liquid crystal projector used in a high heat environment of about 200 ° C. In addition, this Example 37 shown also in Table 1 is a reference example.

(Example 38)
A heat-resistant light-shielding film was prototyped in the same manner as in Example 26, except that the gallium oxide target was changed when the low-reflective oxide film was produced. The gallium oxide film was high frequency sputtering, and a mixed gas of argon and oxygen was used as a sputtering gas. A film having a thickness of 75 μm was used.
When the surface temperature of the film at the time of sputtering was measured by the same method as in Example 1, the temperature was 180 to 220 ° C., which was the same film temperature as in Example 1.
When the obtained light shielding film was evaluated by the same method as in Example 1, it was found that a light shielding film having an optical density of 4 or more, a maximum reflectance of 4% at a wavelength of 380 to 780 nm, and a glossiness of 3% or less was obtained. It was. The heat resistance was also evaluated in the same manner, but the results were exactly the same as in Example 1. Further, it was confirmed that the surface resistance value was 80Ω / □, and the arithmetic average height Ra of the surface was 0.4 μm.
Therefore, such a heat-resistant light-shielding film can be used as a member such as a diaphragm of a liquid crystal projector used in a high heat environment of about 200 ° C.

(Example 39)
A carbon film with a film thickness of 50 nm was used in the same manner as in Example 1 using a Ni-W target when producing a light-shielding metal film and using a titanium target when producing a low-reflective oxide film. A heat-resistant light-shielding film was manufactured by forming a nickel-tungsten film (Ni-WC) containing light-shielding carbon containing Ni and a low-reflective titanium oxide film having a thickness of 80 nm on both sides. A film having a thickness of 50 μm was used, but the type of film and the matting conditions of the film were the same as those in Example 1.
The composition of each film was quantitatively analyzed by EPMA, and it was confirmed that a nickel carbide tungsten film and a titanium oxide film were obtained.
When the surface temperature of the film at the time of sputtering was measured by the same method as in Example 1, the temperature was 180 to 220 ° C., which was the same film temperature as in Example 1.
When the obtained light shielding film was evaluated by the same method as in Example 1, it was found that a light shielding film having an optical density of 4 or more, a maximum reflectance of 5% at a wavelength of 380 to 780 nm, and a glossiness of 3% or less was obtained. It was. The heat resistance was also evaluated in the same manner, but the results were exactly the same as in Example 1. Further, it was confirmed that the surface resistance value was 800Ω / □, and the arithmetic average height Ra of the surface was 0.4 μm.
Therefore, such a heat-resistant light-shielding film can be used as a member such as a diaphragm of a liquid crystal projector used in a high heat environment of about 200 ° C.

(Example 40)
A Ni-W target is used when producing a light-shielding metal film, a Ti target is used when producing a low-reflective oxide film, and nitrogen gas is added to Ar gas in the same manner as in Example 1. And a Ni-W film containing light-shielding nitrogen with a thickness of 100 nm and a low-reflective titanium oxide film with a thickness of 55 nm were formed on both sides to produce a heat-resistant light-shielding film. A film having a thickness of 75 μm was used.
When the surface temperature of the film at the time of sputtering was measured by the same method as in Example 1, the temperature was 180 to 220 ° C., which was the same film temperature as in Example 1.
When the obtained light shielding film was evaluated by the same method as in Example 1, it was found that a light shielding film having an optical density of 4 or more, a maximum reflectance of 5% at a wavelength of 380 to 780 nm, and a glossiness of 3% or less was obtained. It was. The heat resistance was also evaluated in the same manner, but the results were exactly the same as in Example 1. Further, it was confirmed that the surface resistance value was 500Ω / □, and the arithmetic average height Ra of the surface was 0.4 μm.
Therefore, such a heat-resistant light-shielding film can be used as a member such as a diaphragm of a liquid crystal projector used in a high heat environment of about 200 ° C.

(Example 41)
In the same manner as in Example 1, a Ni-W target was used when producing a light-shielding metal film, and a cerium oxide target was used when producing a low-reflective oxide film. A heat-resistant light-shielding film was prototyped by forming a light-shielding Ni—W film and a low-reflective cerium oxide film having a thickness of 55 nm on both sides. The Ni—W film was formed by direct current sputtering, and the cerium oxide film was formed by high frequency sputtering. The type of film and the matting conditions of the film are the same as in Example 1.
When the surface temperature of the film at the time of sputtering was measured by the same method as in Example 1, the temperature was 180 to 220 ° C., which was the same film temperature as in Example 1.
When the obtained light shielding film was evaluated by the same method as in Example 1, it was found that a light shielding film having an optical density of 4 or more, a maximum reflectance of 5% at a wavelength of 380 to 780 nm, and a glossiness of 3% or less was obtained. It was. The heat resistance was also evaluated in the same manner, but the results were exactly the same as in Example 1. Further, it was confirmed that the surface resistance value was 15Ω / □, and the arithmetic average height Ra of the surface was 0.4 μm.
Therefore, such a heat-resistant light-shielding film can be used as a member such as a diaphragm of a liquid crystal projector used in a high heat environment of about 200 ° C.

(Example 42)
A heat-resistant light-shielding film was prototyped in the same manner as in Example 41 except that the resin film substrate was changed to a polyimide film having a thickness of 12.5 μm. The surface roughness of the polyimide film is the same as in Example 41.
When the surface temperature of the film at the time of sputtering was measured by the same method as in Example 1, the temperature was 180 to 220 ° C., which was the same film temperature as in Example 1.
When the obtained light shielding film was evaluated by the same method as in Example 1, it was found that a light shielding film having an optical density of 4 or more, a maximum reflectance of 5% at a wavelength of 380 to 780 nm, and a glossiness of 3% or less was obtained. It was. The heat resistance was also evaluated in the same manner, but the results were exactly the same as in Example 1. Further, it was confirmed that the surface resistance value was 15Ω / □, and the arithmetic average height Ra of the surface was 0.4 μm.
Further, it was found that even when only the thickness of the polyimide film was changed to 25 μm and 38 μm, a heat-resistant light-shielding film having the same characteristics was obtained.
Therefore, such a heat-resistant light-shielding film can be used as a member such as a diaphragm of a liquid crystal projector used in a high heat environment of about 200 ° C.

(Example 43)
Except for changing the sputtering gas pressure to 0.2 Pa using a Ni-W target when producing a light-shielding metal film and using a Ti target when producing a low-reflective oxide film. In the same manner as in Example 1, a heat-resistant light-shielding film was fabricated by forming a light-shielding Ni—W film having a thickness of 100 nm and a low-reflective titanium oxide film having a thickness of 50 nm on both surfaces. The type of film and the matting conditions of the film are the same as in Example 1.
When the surface temperature of the film at the time of sputtering was measured by the same method as in Example 1, the temperature was 180 to 220 ° C., which was the same film temperature as in Example 1.
When the obtained light-shielding film was evaluated in the same manner as in Example 1, it was found that a light-shielding film having an optical density of 4 or more, a maximum reflectance of 1% at a wavelength of 380 to 780 nm, and a glossiness of 3% or less was obtained. It was. The heat resistance was also evaluated in the same manner, but the results were exactly the same as in Example 1. Further, it was confirmed that the surface resistance value was 300Ω / □, and the arithmetic average height Ra of the surface was 0.4 μm.
Therefore, such a heat-resistant light-shielding film can be used as a member such as a diaphragm of a liquid crystal projector used in a high heat environment of about 200 ° C.
Similar results were obtained when only the gas pressure during film formation was 0.5 Pa, 0.7 Pa, or 1.0 Pa.

(Example 44)
Except for changing the sputtering gas pressure to 1.2 Pa using a Ni-W target when producing a light-shielding metal film and using a Ti target when producing a low reflective oxide film. In the same manner as in Example 1, a heat-resistant light-shielding film was fabricated by forming a light-shielding Ni—W film having a thickness of 100 nm and a low-reflective titanium oxide film having a thickness of 50 nm on both surfaces. The type of film and the matting conditions of the film are the same as in Example 1.
When the surface temperature of the film at the time of sputtering was measured by the same method as in Example 1, the temperature was 180 to 220 ° C., which was the same film temperature as in Example 1.
When the obtained light-shielding film was evaluated by the same method as in Example 1, a light-shielding film equivalent to Example 1 with an optical density of 4 or more, a maximum reflectance of 1% at a wavelength of 380 to 780 nm, and a glossiness of 3% or less was obtained. I found out. Further, the surface resistance value was 300Ω / □, and the arithmetic average height Ra of the surface was 0.4 μm. However, in the adhesion test after the heat resistance test, the film was slightly peeled off.
Therefore, although such a heat-resistant light-shielding film can be used for many optical applications, it has been found that the heat-resistant light-shielding film is not suitable as a member such as a diaphragm of a liquid crystal projector used in a high heat environment of about 200 ° C.

(Example 45)
Using a Ni-Cu target when producing a light-shielding metal film and using a Cu target when producing a low-reflective oxide film, in the same manner as in Example 1, the light-shielding Ni-Cu target is used. A heat-resistant light-shielding film was fabricated by forming a film and a low-reflective copper oxide film on both sides. The type of film and the matting conditions of the film are the same as in Example 1.
When the surface temperature of the film at the time of sputtering was measured by the same method as in Example 1, the temperature was 180 to 220 ° C., which was the same film temperature as in Example 1.
When the obtained light-shielding film was evaluated in the same manner as in Example 1, it was found that a light-shielding film having an optical density of 4 or more, a maximum reflectance of 1% at a wavelength of 380 to 780 nm, and a glossiness of 3% or less was obtained. It was. The heat resistance was also evaluated in the same manner, but the results were exactly the same as in Example 1. Further, it was confirmed that the surface resistance value was 100Ω / □, and the arithmetic average height Ra of the surface was 0.4 μm.
Therefore, such a heat-resistant light-shielding film can be used as a member such as a diaphragm of a liquid crystal projector used in a high heat environment of about 200 ° C.

(Comparative Example 1)
The light shielding film was produced by changing the surface processing conditions of the polyimide film by sandblasting. That is, a heat-resistant light-shielding film having the same film configuration was produced under the same conditions as in Example 1 except that a polyimide film having an arithmetic average height Ra of 0.1 μm was used. However, the kind and thickness of polyimide are the same as those in Example 1.
When the surface temperature of the film at the time of sputtering was measured by the same method as in Example 1, the temperature was 180 to 220 ° C., which was the same film temperature as in Example 1.
Evaluation (optical characteristics, heat resistance) of the produced heat-resistant light-shielding film was carried out under the same method and conditions as in Example 1. As a result, an optical density of 4 or more was obtained, which was the same as in Example 1. However, the light reflectance at a wavelength of 380 to 780 nm was 8% at the maximum, and the glossiness was 6%. It was a heat-resistant light-shielding film with a high rate and glossiness. Further, it was confirmed that the surface resistance value was 500Ω / □, and the arithmetic average height Ra of the surface was less than 0.1 μm. In the adhesion evaluation of the film after the heating test at 220 ° C. for 24 hours, there was no warpage or film peeling. The construction and characteristics of the heat-resistant light-shielding film thus produced are summarized in Table 1.
Even if such a heat-resistant light-shielding film having a large value of reflectance or gloss is used for a shutter blade or the like, it is difficult to use it because it is affected by surface reflection.

(Comparative Example 2)
A heat-resistant light-shielding film having the same film configuration was produced under exactly the same conditions as in Example 1 except that a polyimide film having an arithmetic average height Ra of 1.0 μm produced by changing the surface processing conditions by sandblasting was used. However, the kind and thickness of polyimide are the same as those in Example 1.
When the surface temperature of the film at the time of sputtering was measured by the same method as in Example 1, the temperature was 180 to 220 ° C., which was the same film temperature as in Example 1.
Evaluation (optical characteristics, heat resistance) of the produced heat-resistant light-shielding film was carried out under the same method and conditions as in Example 1. As a result, the reflectance was 1% or less and the glossiness was 2% or less, and the same one as in Example 2 was obtained. However, the optical density was 2, and the heat-resistant light-shielding lightness was lower than that in Example 1. It was a film. Further, it was confirmed that the surface resistance value was 500Ω / □, and the arithmetic average height Ra of the surface was 0.9 μm. In the adhesion evaluation of the film after the heating test at 220 ° C. for 24 hours, there was no warpage or film peeling. The construction and characteristics of the heat-resistant light-shielding film thus produced are summarized in Table 1.
Therefore, such a heat-resistant light-shielding film having a low optical density transmits a considerable amount of light as compared with the embodiment, and therefore cannot be used not only for a diaphragm member of a liquid crystal projector but also for many optical system light-shielding applications.

(Comparative Example 3)
Using a Ni-W target, a light-shielding film was produced under the same conditions and configuration as in Example 1 except that a PET film was used as a resin film without matting. When the surface temperature of the film at the time of sputtering was measured by the same method as in Example 1, the temperature was 180 to 220 ° C., which was the same film temperature as in Example 1.
The obtained light-shielding film has an optical density of 3, a maximum reflectance of 12%, a glossiness of 90%, a surface resistance of 400Ω / □, and an arithmetic average height Ra of 0 on the surface. Confirmed to be 5 μm. It has been found that surface waviness and wrinkles are generated, making it unsuitable as a blade member for a diaphragm of a liquid crystal projector used in a high heat environment of about 200 ° C.
Similar results were obtained when a PEN film or a PC film was used as the resin film.

(Comparative Example 4)
The cooling temperature of the can roll that cools the film base material during film formation was set to 50 ° C., and the input power to the target was set to 50% of Example 1 so that the film base material temperature during film formation was less than 180 ° C. Except for the above, a heat-resistant light-shielding film was produced by the same method and structure as in Example 1. It was 140-160 degreeC when the surface temperature of the film at the time of sputtering was measured by the method similar to Example 1. FIG.
Evaluation (optical characteristics, heat resistance) of the produced heat-resistant light-shielding film was carried out under the same method and conditions as in Example 1. As a result, the optical density was 2, the maximum reflectance was 6%, and the glossiness was 7%. Further, it was confirmed that the surface resistance value was 600Ω / □, and the arithmetic average height Ra of the surface was 0.5 μm. Moreover, in the adhesion evaluation of the film after the heating test at 220 ° C. for 24 hours, the warpage was large and the adhesion of the film was very bad. The construction and characteristics of the heat-resistant light-shielding film thus produced are summarized in Table 1.
Therefore, such a heat-resistant light-shielding film having poor optical density, reflectance, glossiness, and adhesiveness has poor optical properties such as optical density, reflectance, and glossiness, and has no adhesiveness. It cannot be used for many optical system applications.

(Comparative Example 5)
Using a Ni-W target when producing a light-shielding metal film and using a Ti target when producing a low-reflective oxide film, a light-shielding film with a thickness of 30 nm is used in the same manner as in Example 1. A heat-resistant light-shielding film was fabricated by forming a functional Ni—W film and a low-reflective titanium oxide film having a thickness of 55 nm on both sides. The Ni—W film and the titanium oxide film were formed by a direct current sputtering method. For the Ni—W film, only argon was used as the sputtering gas, and for the titanium oxide film, a mixed gas of argon and oxygen was used as the sputtering gas. A film having a thickness of 75 μm was used.
When the surface temperature of the film at the time of sputtering was measured by the same method as in Example 1, the temperature was 180 to 220 ° C., which was the same film temperature as in Example 1.
When the obtained light-shielding film was evaluated by the same method as in Example 1, the maximum reflectance at a wavelength of 380 to 780 nm was 5% and the glossiness was 3% or less, but the optical density was 2, and light was slightly emitted. Permeation was confirmed. Further, the heat resistance was evaluated in the same manner, but the result was exactly the same as in Example 1. Further, it was confirmed that the surface resistance value was 15Ω / □, and the arithmetic average height Ra of the surface was 0.4 μm.
Therefore, such a heat-resistant light-shielding film having a low optical density transmits a slight amount of light, and is not preferable as a member such as a diaphragm of a liquid crystal projector.

(Comparative Example 6)
A heat-resistant light-shielding film was produced in the same manner as in Example 1 except that only the metal film was formed without forming the oxide film. Similarly to Example 1, when the metal film was sputtered, the surface temperature of the film was measured from the observation window of the quartz glass of the take-up type sputtering apparatus with an infrared radiation thermometer, and the temperature was 180 to 220 ° C.
The obtained heat-resistant light-shielding film has a surface arithmetic average height Ra of 0.4 μm, an optical density of 4 or more, a surface resistance value of 210 Ω / □, and has sufficient light-shielding properties and conductivity. Was. However, the maximum reflectance was 12% and the glossiness was high at 16%. This is because the surface is a highly reflective metal film. Since the reflectance is high, the reflected light becomes stray light when used as an optical member of the lens unit, which is not preferable.
Moreover, when the scratch hardness test (pencil method) was performed based on JIS K5600-5-4, it was HB level and hardness was inferior compared with all the above-mentioned Examples (H or more). This is because in Comparative Example 6, the surface is a metal film, but in the examples, it is an oxide film having hardness. Therefore, when used as a light amount adjusting device or a blade material of a shutter, the blade materials rub against each other and scratches the film, which gradually deteriorates the light shielding property.
Further, in the evaluation of the adhesion of the film after the heating test at 220 ° C. for 24 hours, the film peeling was remarkably observed. This is because the metal film is oxidized. The optical density after film peeling occurred was 3, and the coefficient of friction was poor.
Such a heat-resistant light-shielding film cannot be used as a light-shielding member used at room temperature, and is naturally unsuitable as a blade member such as a diaphragm of a liquid crystal projector used in a high heat environment of about 200 ° C.

(Example 46)
Using a polyimide film having a thickness of 38 μm and an arithmetic average height of Ra of 0.5 μm on both sides, a nickel oxide film having a thickness of 20 nm is formed as a gas barrier film, and a light-shielding metal film having a thickness of 120 nm is formed thereon. A heat-resistant light-shielding film was fabricated using a nickel-based metal film and a titanium oxide film as the low-reflective oxide film.
Using the same film forming apparatus as in Example 1, the gas barrier film and the metal film were formed using a Ni-based alloy target containing Ni as a main component and 6.9 atomic% W, and the titanium oxide film was formed using a metal Ti target. Filmed.
When the surface temperature of the film at the time of sputtering was measured by the same method as in Example 1, the temperature was 180 to 220 ° C., which was the same film temperature as in Example 1.
When the obtained light shielding film was evaluated by the same method as in Example 1, the light shielding film having an optical density of 4 or more, a maximum reflectance of 2% at a wavelength of 380 to 780 nm, a minimum reflectance of 1.5%, and a glossiness of 3% or less. It was found that was obtained. The heat resistance was also evaluated in the same manner, but the results were exactly the same as in Example 1. Further, it was confirmed that the surface resistance value was 300Ω / □, and the arithmetic average height Ra of the surface was 0.4 μm.
Further, this heat-resistant light-shielding film was subjected to a constant temperature and humidity test for 1000 hours at 85 ° C. and 90% RH, but there was no change in color. When spectroscopic measurement was performed at a wavelength of 380 to 780 nm, the maximum reflectance and the minimum reflectance were not changed.
Therefore, such a heat-resistant light-shielding film can be used as a member such as a diaphragm of a liquid crystal projector used in a high heat environment of about 200 ° C.
Further, this heat-resistant light-shielding film was subjected to a constant temperature and humidity test for 1000 hours at 85 ° C. and 90% RH, but the reflectance, color, and surface resistance did not change.

(Example 47)
A heat-resistant light-shielding film was produced by the same method and structure as in Example 46 except that the gas barrier film was not inserted between the resin film substrate and the metal film. When the surface temperature of the film at the time of sputtering was measured by the same method as Example 1, it was 180-220 degreeC.
When the obtained light shielding film was evaluated by the same method as in Example 1, the light shielding film having an optical density of 4 or more, a maximum reflectance of 2% at a wavelength of 380 to 780 nm, a minimum reflectance of 1.5%, and a glossiness of 3% or less. It was found that was obtained. The heat resistance was also evaluated in the same manner, but the results were exactly the same as in Example 1. Further, it was confirmed that the surface resistance value was 300Ω / □, and the arithmetic average height Ra of the surface was 0.4 μm.
Therefore, such a heat-resistant light-shielding film can be used as a member such as a diaphragm of a liquid crystal projector used in a high heat environment of about 200 ° C.
Further, when this thermostable light-shielding film was subjected to a constant temperature and humidity test at 85 ° C. and 90% RH for 1000 hours, a slight change in color was observed, and the color changed from black to dark dark blue. When spectroscopic measurement was performed at a wavelength of 380 to 780 nm, it was found that the maximum reflectance increased to 5% and the minimum reflectance decreased to 0.2%. When cross-sectional TEM observation of the heat-resistant light-shielding film after the test and local composition analysis by EDX were performed, it was found that about 3% of oxygen entered a part of the metal film on the resin film side. Since the metal film has a two-layer structure with different optical characteristics as described above, it is considered that the change in reflectance as described above was observed.
Even if there is such a color change, the maximum reflectance is 5% or less, and it can be used sufficiently. However, as an application that dislikes the color change, as shown in Example 47, a gas barrier film is used. Is useful to insert.

(Example 48)
As a gas barrier film inserted in Example 46, a heat-resistant light-shielding film was prototyped instead of a silicon oxide film (film thickness: 30 nm), and a constant temperature and humidity test was performed at 85 ° C. and 90% RH for 1000 hours. It has been found that there is no change in color and reflectance, and it functions effectively as a gas barrier film. Tantalum oxide (film thickness 10 nm), tungsten oxide (film thickness 10 nm), vanadium oxide (film thickness 30 nm), molybdenum oxide (film thickness 20 nm), cobalt oxide (film thickness 10 nm), niobium oxide (film thickness 10 nm) The same was true for iron oxide (film thickness 10 nm), aluminum oxide (film thickness 30 nm), or titanium oxide film (film thickness 5 nm, 30 nm).

(Example 49)
The heat-resistant light-shielding film produced in Examples 1 to 48 was punched to produce 20 mm × 30 mm light-shielding blades. The weight of one light shielding blade was 0.007 to 0.02 g. Two light-shielding blades were mounted on an aperture device and a durability test was performed.
In the durability test, the light shielding blade is operated by repeating the range of the maximum and minimum opening diameters in the operating range of the light shielding blade tens of thousands of times while irradiating the lamp light. evaluated.
There was no change in the appearance of the light-shielding blade due to wear due to the test, and no foreign matter adhered to the diaphragm device due to wear. Therefore, the friction, wear and noise are small, and the weight is reduced by using the resin film as a base material, and the driving torque of the motor for driving the light shielding blade can be reduced, and the slidability is good.

(Comparative Example 7)
Except for changing the light-shielding blade to a metal SUS thin plate having a thickness of 50 μm, 75 μm, or 150 μm, the light-shielding film was punched in the same manner as in Example 49, and the light-shielding blade of 20 mm × 30 mm using the SUS thin plate as a base material The same evaluation as in Example 49 was performed. The weight of the light shielding blade was 0.2 to 0.6 g, which was heavier than the weight of the light shielding blade of the same shape using the heat-resistant light shielding film of Example 49 of the present invention.
There was no change in the appearance of the light-shielding blade due to wear due to the test, and no foreign matter adhered to the diaphragm device due to wear. However, since the weight of the light shielding blade is large, the driving torque of the motor that drives the light shielding blade is increased, and the slidability is poor.

It is sectional drawing of the heat-resistant light-shielding film of this invention. It is a schematic diagram which shows an example of the winding-type sputtering apparatus used in manufacturing the heat-resistant light-shielding film of this invention. It is a schematic diagram which shows the aperture mechanism of the aperture device for light quantity adjustment using the heat-resistant light-shielding film of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Resin film base material 2 Light-shielding metal film 3 Low reflective oxide film 4 Unwinding roll 5 Vacuum pump 6 Vacuum tank 7 Cooling can roll 8 Winding roll 9 Magnetron cathode 10 Target 11 Partition 12 Heat-resistant light-shielding blade 13 Guide Hole 14 Guide pin 15 Pin 16 Substrate 17 Hole 18 Opening

Claims (20)

A resin film substrate (A) having a heat resistance of 200 ° C. or higher, and a Ni-based metal film (B) having a thickness of 50 nm or more formed on one or both surfaces of the resin film substrate (A) by a sputtering method; And selected from the group consisting of titanium, tantalum, tungsten, vanadium, molybdenum, cobalt, niobium, iron, copper, zinc, aluminum, silicon, gallium and cerium formed on the Ni-based metal film (B) by sputtering. In addition, the Ni-based metal film (B) has a film thickness of 50 to 250 nm, and the oxide film (C). A heat-resistant light-shielding film , wherein the film thickness is 5 to 240 nm and the surface roughness of the laminated film is 0.1 to 0.7 μm (arithmetic average height Ra).   The resin film substrate (A) is composed of one or more organic resins selected from polyimide, aramid, polyphenylene sulfide, or polyether sulfone, and has a surface roughness of 0.2 to 0.8 μm (arithmetic average) The heat-resistant light-shielding film according to claim 1, which has a height Ra).   The Ni-based metal film (B) has at least one selected from the group consisting of titanium, tantalum, tungsten, vanadium, molybdenum, cobalt, niobium, iron, copper, zinc, aluminum, and silicon, with nickel as the main component. The heat-resistant light-shielding film according to claim 1, which is a nickel-based alloy film containing an additive element. Heat shielding film according to any one of claims 1 to 3, wherein the surface resistance of the laminated film is 1 × 10 ⁴ Ω / □ or less. Heat shielding film according to claim 1-4, wherein the light reflectance of the laminated film, characterized in that less than 5% at a wavelength of 380 to 780 nm. A laminated film composed of a Ni-based metal film (B) and an oxide film (C) is formed on both surfaces of the resin film substrate (A), and has a symmetrical structure with the film substrate as the center. The heat-resistant light-shielding film in any one of Claims 1-5 .   7. The metal oxide film formed by a sputtering method is interposed as a gas barrier film (D) at the interface between the resin film substrate (A) and the metal film (B). Heat-resistant light-shielding film. The gas barrier film (D) is an oxide film containing as a main component one or more elements selected from the group consisting of titanium, tantalum, tungsten, vanadium, molybdenum, cobalt, niobium, iron, aluminum, silicon, and nickel. The heat-resistant light-shielding film according to claim 7 . A laminated film composed of a gas barrier film (D), a metal film (B), and an oxide film (C) is formed on both surfaces of the resin film substrate (A), and has a symmetrical structure with the film substrate as the center. The heat-resistant light-shielding film according to claim 7 or 8 . The gas barrier films (D), metal films (B), and oxide films (C) formed on both surfaces of the resin film substrate (A) have substantially the same metal element composition. The heat-resistant light-shielding film according to claim 7 . A resin film base material (A) having an uneven surface with a surface roughness of one or both sides of 0.2 to 0.8 μm (arithmetic average height Ra) is supplied to a sputtering apparatus, and using a metal film forming target, Reactive sputtering in which an Ni-based metal film (B) is formed on the uneven surface of the resin film substrate (A) by sputtering, and then oxygen gas is introduced into the sputtering gas using a target for forming an oxide film Thus, on the Ni-based metal film (B), at least one selected from the group consisting of titanium, tantalum, tungsten, vanadium, molybdenum, cobalt, niobium, iron, copper, zinc, aluminum, silicon, gallium and cerium An oxide film (C) containing an element is formed. The method for producing a heat-resistant light-shielding film according to any one of claims 1 to 6 . Sputtering gas pressure is 0.2-1.0Pa, The manufacturing method of the heat-resistant light-shielding film of Claim 11 characterized by the above-mentioned. The method for producing a heat-resistant light-shielding film according to claim 11 or 12 , wherein the resin film substrate temperature during sputtering is 180 ° C or higher. The heat-resistant light-shielding film on which the Ni-based metal film (B) and the oxide film (C) are formed is further supplied to a sputtering apparatus, and a Ni-based metal film (on the back surface of the resin film substrate (A) is formed by sputtering. B) and an oxide film (C) containing one or more elements selected from the group consisting of titanium, tantalum, tungsten, vanadium, molybdenum, cobalt, niobium, iron, copper, zinc, aluminum, silicon, gallium, and cerium ) Are formed sequentially, The manufacturing method of the heat-resistant light-shielding film in any one of Claims 11-13 characterized by the above-mentioned. Supplying a resin film substrate (A) having an uneven surface with a surface roughness of 0.2 to 0.8 μm (arithmetic average height Ra) on one or both sides to a sputtering apparatus, using a gas barrier film forming target, The gas barrier film (D) is first formed on the uneven surface of the resin film substrate (A) by sputtering, and then the metal film (B) and the oxide film (C) are sequentially formed. The manufacturing method of the heat-resistant light-shielding film of claim | item 7-10 . The film according to claim 15 , wherein the gas barrier film forming target and the metal film forming target, or the gas barrier film forming target and the oxide film forming target are the same, and each film is formed. The manufacturing method of the heat-resistant light-shielding film of description. The method for producing a heat-resistant light-shielding film according to any one of claims 11 to 16 , wherein the resin film substrate (A) is wound into a roll and set in a film transport unit of a sputtering apparatus. The method for producing a heat-resistant light-shielding film according to any one of claims 11 to 16 , wherein the resin film substrate during film formation is formed by sputtering in a floating state in the film formation chamber without being cooled. A diaphragm excellent in heat resistance, produced by processing the heat-resistant light-shielding film according to any one of claims 1 to 10 . The light quantity adjustment apparatus which uses the heat-resistant light-shielding film in any one of Claims 1-10 as a blade | wing material.

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