JP2012203310A - Heat-resistant light-shielding multilayer film, production method of the same, and application - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat-resistant light-shielding film, which maintains high light-shielding property, low reflecting property of the surface, low surface glossiness and blackness even in a high temperature environment at 100°C in air, suppresses changes with time in a film color on the film surface, and can be used for a fixed diaphragm, a shutter blade, a diaphragm blade of a luminous energy controlling device, a heat-resistant light-shielding tape, or the like.SOLUTION: The heat-resistant light-shielding film includes: a resin film (A) as a substrate having heat resistance against 100°C or higher and having a fine rugged pattern with an arithmetic average height Ra of 0.2 to 2.2 μm formed on the surface; and on one surface or both surfaces of the substrate, the following films are successively formed: a metal light-shielding film (B) as a first layer; a black coating film (C) as a second layer essentially comprising titanium and oxygen with an O/Ti atom ratio of 0.7 to 1.4 in the film; and a transparent metal compound film (D) as a third layer. The film (D) comprises an oxide, nitride oxide, carbide oxide, or carbide nitride oxide of one or more elements selected from aluminum, titanium, silicon, zinc, indium, gallium, tin and magnesium.

Description

  The present invention relates to a heat-resistant and light-shielding multilayer film, a method for producing the same, and uses, and more particularly, in shutter blades or diaphragm blades such as lens shutters of digital cameras and digital video cameras, and in lens units of camera-equipped mobile phones and vehicle monitors Heat-resistant light-shielding multilayer film with excellent light-shielding properties, low-reflective properties, and low surface glossiness, and its use as optical device parts such as fixed apertures and diaphragm blades for projector light-amount adjusting devices (also called auto iris) The present invention relates to a manufacturing method and an application.

  In recent years, high-speed (mechanical) shutters for digital cameras have been actively developed. The aim is to increase the shutter speed and to shoot a very high-speed subject without blurring and to obtain a clear image. In general, the shutter is opened and closed by rotating and moving a plurality of blades called shutter blades, but in order to increase the shutter speed, the shutter blades can respond to instantaneous operation and stop, It is essential to be lightweight and highly slidable. Furthermore, since the shutter blades have a role of blocking light by covering the front surface of a photosensitive material such as a film or an image pickup device such as a CCD or CMOS in a state where the shutter is closed, the shutter blade needs to be completely shielded from light. In addition, when a plurality of shutter blades overlap each other to operate, the regular reflectance of the shutter blade surface is low to prevent leakage light between the shutter blades, that is, the blackness of the surface color is high. It is desirable.

  Even with a fixed aperture that is inserted into the lens unit of a digital camera and serves to send light to the image sensor with a fixed amount of light, stray light is generated due to reflection on the surface of the fixed aperture, enabling clear imaging. Therefore, the surface is required to have low reflectivity, that is, high blackness.

Also in mobile phones having a photographing function, that is, camera-equipped mobile phones, in recent years, a small mechanical shutter has begun to be mounted on a lens unit so that high-quality images can be taken with high pixels, like a digital camera. A fixed aperture is also inserted into the lens unit of the mobile phone. The mechanical shutter incorporated in the above mobile phone must operate with a smaller electric power than a general digital camera, and therefore, the weight reduction of the shutter blade is particularly strongly required.
The lens unit of a digital camera or a mobile phone is often assembled using an ultraviolet curable resin. Recently, in a lens unit of a camera-equipped cellular phone, assembling of members such as a lens, a fixed aperture, and a shutter blade is often performed in a reflow process in order to reduce manufacturing costs. For this reason, not only the low reflectivity and blackness of the surface but also the heat resistance has become important for the fixed aperture and shutter blades used for this purpose.
This reflow process has been put into practical use with the goal of reducing the size and height of camera modules mounted on recent digital cameras, mobile phones with cameras, and simplifying the manufacturing process. In addition, with the practical use of the reflow process, the wafer / All components are assembled in a wafer state, called level chip size package (hereinafter referred to as WLCSP), where each component is not separated into individual chips, and mounted on a circuit board using die bonding, solder balls, After the process is completed, the process is shifted to a manufacturing method in which the product is individually diced into chip sizes to obtain a finished product. Since WLCSP can reduce the number of parts, it is an effective process for reducing the size and height of a camera module.

  In addition to the leakage light from the front surface of the image sensor such as CCD and CMOS, when the flexible printed wiring board (hereinafter referred to as FPC) becomes thinner, the light incident from the FPC side on the back surface of the image sensor is also received. There is a problem that it cannot be ignored. The incident light from the back surface of the image pickup device causes the FPC wiring circuit to appear in the image pickup area and deteriorates the quality of image pickup. Therefore, it is necessary to shield the leaked light from the FPC side.

  Also, as a recent trend of equipment mounted on automobiles, monitors using video cameras such as back view monitors tend to be installed. A fixed aperture is also used in the lens unit of this video camera monitor. Similarly, in order to prevent stray light, low reflectivity and blackness are required for the characteristics of the surface of the aperture. In addition, the lens unit of an in-vehicle video camera must have sufficient heat resistance so that its function is not impaired even under high-temperature use environments such as under the hot summer sun. The fixed diaphragm member is required to have heat resistance as well. The

  On the other hand, a liquid crystal projector can be viewed as a home theater with a large screen, and has recently begun to spread to ordinary households. There has been a strong demand for high image quality that enables bright high-contrast images to be enjoyed even in a bright environment such as a living room. By increasing the output of the lamp light source, the image quality is increased. In the optical system of the projector, a light amount adjusting diaphragm device (auto iris) for adjusting the light amount from the lamp light source is used in the lens system or on the side surface. In the light quantity adjusting diaphragm device, similarly to the shutter, a plurality of diaphragm blades overlap each other to change the area of the opening and adjust the light quantity. The diaphragm blades of such a light quantity adjusting diaphragm device are also required to have low surface reflection and weight reduction for the same reason as in the case of the shutter blades. This is because if the low reflectivity of the blade material is impaired by light irradiation, stray light is generated and a clear image cannot be taken. At the same time, the diaphragm blades of the light quantity adjusting diaphragm device need to have heat resistance against heating by irradiation with lamp light.

The above-described fixed diaphragm, shutter blade, and diaphragm blade of the light amount adjusting diaphragm device are generally used as light shielding plates in accordance with required characteristics.
When heat resistance is required, a light shielding plate based on a metal thin plate such as SUS, SK material, Al, Ti or the like is generally used. Although there is a metal thin plate itself as a light shielding plate, it has a metallic luster, which is not preferable when it is desired to avoid the influence of stray light due to reflected light on the surface. On the other hand, a light shielding plate coated with black lubricant on a thin metal plate has low reflectivity and blackness, but the coated part is inferior in heat resistance. In order to suppress this, after processing into a predetermined shape, a process of blackening the processed end face is essential, and there is a problem that the manufacturing cost increases.
Patent Document 1 proposes 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. However, the surface formation of the hard carbon film cannot achieve low reflection characteristics, and the generation of stray light due to reflected light is inevitable. Moreover, in patent document 2, on the metal base-material surface,
There has been proposed a light shielding material in which an anodized film is formed and a light reflection reducing layer is provided by depositing a metal into the micropores formed in the film by an electrolytic coloring method. However, the anodization treatment has a large variation in film thickness, and the film thickness is as thick as several μm, making it difficult to control the thickness. Not applicable to
In any of the above cases, when a light shielding plate using a thin metal plate as a base material is used as a shutter blade or a diaphragm blade, the weight is large, so the torque of the drive motor that drives the blade increases and the power consumption increases. There are problems that the speed cannot be increased and noise is generated due to contact between blades.

  On the other hand, the light-shielding plate which used the resin film as a base material and provided the reduction of the reflection by surface treatment is also proposed. Patent Document 3 proposes a light-shielding plate that uses a matte-processed resin film to reduce surface reflection, and a film-shaped light-shielding plate that has been given mattness by forming a large number of fine irregular surfaces. Has been. Patent Document 4 proposes a light-shielding film in which a thermosetting resin containing a matte paint is coated on a resin film.

  As for a light shielding plate using a resin film as a base material, a light shielding plate using polyethylene terephthalate (PET) as a base material is widely used because of its low specific gravity, low cost, and flexibility.

However, the heat resistance of the PET material is as low as about 105 ° C. and the mechanical strength such as tensile elastic modulus is weak. Therefore, when the usage environment exceeds 105 ° C., the light quantity adjustment diaphragm of the projector that is irradiated with high output lamp light It cannot be used as an aperture blade for a device or a fixed aperture or a shutter blade corresponding to a reflow process. In addition, when viewed as a blade portion of a high-speed shutter, the film thickness is reduced according to the increase in the speed of the shutter blade. When it becomes thinner to the following, the black pigment contained in the resin film must be reduced to maintain the mechanical strength of the film, and the blackness obtained by the thick film cannot be exhibited sufficiently. Cannot be maintained, and cannot be used for fixed diaphragms, shutter blades, and diaphragm blades for light quantity adjusting diaphragm devices.
On the other hand, in Patent Document 5, a thin film made of a single metal, a mixture or a compound formed on a resin film by a sputtering method or the like, and a single element or compound of a specific element satisfying the characteristics of conductivity, lubricity and scratch resistance A light shielding blade material obtained by sequentially laminating a thin film (protective film) made of the above has been proposed. Here, there is no mention of low reflectivity and blackness, which are characteristics required for recent light-shielding blades. Further, the effect of the protective film only specifically shows the effect of carbon on the scratch resistance.
As mentioned above, there are coating film materials for reducing the reflection and blackening of the surfaces of optical components such as fixed diaphragms, shutter blades, and diaphragm blades of light quantity adjustment diaphragm devices. It was not put out.
Under such circumstances, a SUS, SK material, Al, Ti, or other thin metal plate or a resin film with low reflectivity and blackness is used as the base material, and the drive motor that drives the blades is used. Torque and power consumption are not increased, shutter speed is increased, noise is not generated due to contact between blades, fixed aperture and shutter that have both sufficient light shielding and low reflection in the visible range, light weight, and conductivity A blade, a diaphragm blade of a light quantity adjusting diaphragm device, and a light shielding tape have been required.

  Conventionally, in applications where heat resistance is required, it has been necessary to use a metal thin plate, that is, a metal thin plate made of SUS, SK material, Al, Ti, or the like, because sufficient performance cannot be obtained with a resin film. However, because the metal thin plate is heavy, the torque and power consumption of the drive motor that drives the blades increase, or the shutter speed cannot be increased, and noise due to contact between the blades is generated. In addition, there is a problem that the manufacturing cost increases because the processed end face is black-dyed.

  Therefore, the present applicant is required to apply a heat resistant resin film substrate (A) such as polyimide and titanium oxide having a film thickness of 50 nm or more formed by sputtering on one or both surfaces of the resin film substrate (A). A metal light-shielding film (B) made of titanium carbide oxide and an oxygen content formed by sputtering on the metal light-shielding film (B) is 0.7 to 1.4 as an O / Ti atomic ratio. A heat-resistant light-shielding film composed of a carbonized titanium oxide film having a carbon content of 0.7 or more as the C / Ti atomic ratio was proposed. (See Patent Document 6). Thereby, it was possible to obtain a heat-resistant light-shielding film excellent in light-shielding property, heat resistance, slidability, low surface glossiness, and conductivity.

However, although the obtained heat-resistant light-shielding film did not affect the heat resistance and blackness even when left in the atmosphere for 2 weeks, there was a problem that the color of the titanium carbide film on the surface layer changed. Occurred. In this case, the amount of color change can be evaluated by the color difference (ΔE ^* ab) represented by L ^* a ^* b ^* color system measurement (JISZ8729), which is standardized by the CIE (International Commission on Illumination). It was found that the color difference was 2 or more. However, even though it can still be used as a shutter blade or diaphragm blade such as a lens shutter of a digital camera or a digital video camera, or as a fixed diaphragm such as a camera-equipped mobile phone, further stability of quality is desired.

Japanese Patent Laid-Open No. 2-116837 JP 2007-292951 A JP-A-1-120503 JP 4-9802 A JP 2006-138974 A WO2010 / 026683 gazette

  In view of these conventional problems, the present invention maintains high light-shielding property, low surface reflection, low surface glossiness, and blackness even in a high temperature environment of 100 ° C. in the atmosphere, and further the film color of the film surface over time. It is an object of the present invention to provide a heat-resistant light-shielding film that can be used as a fixed diaphragm and shutter blades that can suppress changes, diaphragm blades of a light quantity adjusting diaphragm device, heat-resistant light-shielding tape, and the like, and a method for manufacturing the same.

  In the heat-resistant light-shielding film in which the specific titanium carbide oxide film (black coating film) is formed on the above-described metal light-shielding film, the inventor has a high temperature when the titanium carbide oxide film has a film structure that easily takes in oxygen. As a result of ascertaining that the titanium carbide oxide film oxidizes and changes in color when heated for a long time, and further earnestly researched, the film was formed by forming a transparent metal compound film on the black coating film. It is possible to suppress color change over time, and it has been found that it can maintain high light-shielding properties, low surface reflectivity, low surface glossiness, and blackness even in a high temperature environment of 270 ° C or higher in the atmosphere. The present invention has been completed by confirming that it can be used as a diaphragm or blade member for telephones, digital video cameras, liquid crystal projectors and the like.

  That is, according to the first invention of the present invention, the resin film (A) having a heat resistance of 100 ° C. or higher and having a surface with an arithmetic mean height Ra of 0.2 to 2.2 μm. And the first layer of the metal light-shielding film (B) and the O / Ti atomic ratio in the film is 0.7 to 1.4. A heat-resistant and light-shielding multilayer film is provided in which a two-layer black coating film (C) and a third-layer transparent metal compound film (D) are sequentially formed.

According to the second invention of the present invention, in the first invention, the transparent metal compound film (D) is one or more selected from aluminum, titanium, silicon, zinc, indium, gallium, tin, and magnesium. Provided is a heat-resistant and light-shielding multilayer film characterized by being an oxide of an element, a nitrided oxide, a carbide oxide, or a carbonitride oxide.
According to the third invention of the present invention, in the first or second invention, the metal content of the transparent metal compound film (D) is less than 0.8 as a metal / oxygen atom number ratio. A heat-resistant and light-shielding multilayer film is provided.
According to a fourth aspect of the present invention, there is provided a heat resistant light-shielding multilayer film according to the first to third aspects, wherein the transparent metal compound film (D) has a thickness of 5 to 250 nm. Is done.
According to the fifth aspect of the present invention, in any one of the first to fourth aspects, when the transparent metal compound film (D) is formed on the optical glass substrate, the parallel light transmittance at a wavelength of 380 to 780 nm. However, the average value is 70% or more, and the average regular reflectance is 20% or less.
According to the sixth invention of the present invention, in the first invention, the metal light-shielding film (B) is selected from titanium, tantalum, tungsten, cobalt, nickel, niobium, iron, zinc, copper, aluminum, and silicon. There is provided a heat-resistant light-shielding multilayer film characterized by being selected from the group consisting of one or more kinds of elements.
According to a seventh aspect of the present invention, there is provided a heat resistant light-shielding multilayer film according to the first aspect, wherein the metal light-shielding film (B) is a titanium carbide film or a titanium carbide oxide film. .
According to the eighth invention of the present invention, in the first invention, the carbon content of the metal light-shielding film (B) is 0.6 or more as a C / Ti atomic ratio, and the oxygen content is A heat-resistant light-shielding film having an O / Ti atomic ratio of 0.4 or less is provided.
According to the ninth aspect of the present invention, there is provided the heat-resistant light-shielding multilayer film according to the first aspect, wherein the metal light-shielding film (B) has a thickness of 40 to 250 nm or more.
According to a tenth aspect of the present invention, there is provided the heat-resistant light-shielding multilayer film according to the first aspect, wherein the black coating film (C) further contains carbon.
According to the eleventh aspect of the present invention, there is provided the heat-resistant light-shielding multilayer film according to the first aspect, wherein the black coating film has a thickness of 50 to 250 nm.
According to the twelfth aspect of the present invention, in the first to eleventh aspects, the resin film (A) is polyimide, polyamideimide, polyphenylene sulfide, polyethylene naphthalate, polyethylene terephthalate, polycarbonate, aramid, polyether ether. Provided is a heat-resistant and light-shielding multilayer film characterized by being a film mainly composed of one or more kinds of resins selected from ketones or polyether sulfones.
According to a thirteenth aspect of the present invention, there is provided the heat resistant light-shielding multilayer film according to the first aspect, wherein the resin film (A) has a thickness of 10 to 250 μm.
According to the fourteenth aspect of the present invention, in any one of the first to thirteenth aspects, substantially the same film thickness and the same thickness are provided on both surfaces of the resin film (A) having heat resistance of 100 ° C. or higher. A heat-resistant light-shielding multilayer film characterized in that a metal light-shielding film (B), a black coating film (C), and a transparent metal compound film (D) having a composition are formed and is symmetrical with respect to the resin film (A). Provided.
According to the fifteenth aspect of the present invention, in the first aspect, the average optical density, which is an indicator of light shielding properties, is 4.0 or more at a wavelength of 380 to 780 nm, and the average regular reflectance is less than 0.3%. A heat-resistant and light-shielding multilayer film is provided.
Furthermore, according to the sixteenth invention of the present invention, in the first or fifteenth invention, in the L ^* a ^* b ^* color system measurement (JISZ8729) standardized by the CIE (International Commission on Illumination), L ^* (lightness) is 20 to 35, and the color difference (ΔE * ab) after being left in the atmosphere for 2 weeks is less than 1.0.

  On the other hand, according to the seventeenth aspect of the present invention, the resin film (A) having a fine surface irregularity with an arithmetic average height Ra of 0.2 to 2.2 μm is supplied to a sputtering apparatus, and in an inert gas atmosphere. Sputtering is performed using a metal light-shielding film target to form a metal light-shielding film (B) on the resin film (A), and then black coating is performed in an inert gas atmosphere under a deposition gas pressure of 1.5 Pa or more. Sputtering using a film-forming target, black on which the O / Ti atomic ratio in the film is 0.7 to 1.4 with titanium, oxygen, and carbon as main components on the metal light-shielding film (B) After forming the coating film (C), sputtering is performed using a transparent metal compound (D) target in an inert gas atmosphere, and selected from aluminum, titanium, silicon, zinc, indium, gallium, tin, and magnesium. A transparent metal compound (D) which is an oxide of one or more elements, a nitride oxide, a carbide oxide, or a carbon nitride oxide, wherein the metal content in the film is less than 0.8 as the metal / oxygen atom number ratio. ) Is formed, and a method for producing a heat-resistant and light-shielding multilayer film is provided.

According to the eighteenth aspect of the present invention, in the seventeenth aspect, the transparent metal compound film (D) is one or more selected from aluminum, titanium, silicon, zinc, indium, gallium, tin, and magnesium. Using any of a metal target, a metal oxide target, a metal carbide target or a metal nitride target containing any of the above elements, oxygen gas or / and nitrogen gas is introduced into the argon gas, and 0.2 to 0.8 Pa There is provided a method for producing a heat-resistant and light-shielding multilayer film, characterized by being formed by sputtering at a film forming gas pressure.
According to the nineteenth aspect of the present invention, in the seventeenth or eighteenth aspect, the film forming gas pressure when forming the metal light-shielding film (B) is 0.2 to 0.8 Pa. A method for producing the heat-resistant and light-shielding multilayer film is provided.
According to the twentieth invention of the present invention, the metal light-shielding film (B) and the black coating film (C) on one side obtained by the method for producing a heat-resistant light-shielding multilayer film of the seventeenth to nineteenth inventions. ) And the transparent metal compound film (D) in order, a heat-resistant light-shielding film comprising a laminated film is supplied to a sputtering apparatus, and sputtering using a metal light-shielding film (B) target in an inert gas atmosphere A metal light-shielding film (B) is formed on the other surface where the laminated film of the resin film substrate (A) is not formed, and then a target for forming a black coating film under an inert gas atmosphere is formed. The black coating film (C) having a ratio of O / Ti atoms in the film of 0.7 to 1.4, mainly composed of titanium, oxygen, and carbon, on the metal light-shielding film (B) by sputtering used. After forming the inert gas Oxides and nitride oxides of one or more elements selected from aluminum, titanium, silicon, zinc, indium, gallium, tin, and magnesium by sputtering using a transparent metal compound (D) formation target in an atmosphere A heat-resistant and light-shielding multilayer film characterized by forming a transparent metal compound (D), which is a carbonized oxide or carbonitride oxide, and has a metal content in the film of less than 0.8 as a metal / oxygen atom ratio A manufacturing method is provided.

On the other hand, according to the twenty-first aspect of the present invention, there is provided a diaphragm having excellent heat resistance obtained by punching the heat-resistant light-shielding multilayer film produced in any one of the first to sixteenth aspects.
According to a twenty-second aspect of the present invention, there is provided the diaphragm according to the twenty-first aspect, which is used for a camera module having a wafer level chip size package (WLCSP) structure.
According to the twenty-third aspect of the present invention, in any one of the first to sixteenth aspects, there is provided a shutter blade excellent in heat resistance obtained by punching a heat-resistant light-shielding multilayer film.
Further, according to the twenty-fourth aspect of the present invention, there is provided a diaphragm blade for adjusting the amount of light, which is excellent in heat resistance, obtained by punching a heat-resistant light-shielding multilayer film produced in any one of the first to sixteenth aspects. Is done.
According to the twenty-fifth aspect of the present invention, there is provided a heat-resistant light-shielding tape comprising an adhesive layer on one side or both sides of the heat-resistant light-shielding multilayer film produced in any one of the first to sixteenth aspects. .

The heat-resistant light-shielding multilayer film of the present invention has a heat resistance of 100 ° C. or higher, a resin film (A) having fine irregularities formed on the surface, a metal light-shielding film (B) as a first layer, and a second layer Since a titanium oxide film (C), which is a black coating film mainly composed of titanium and oxygen, is laminated and a transparent metal compound film (D) is sequentially formed as a third layer, a visible light region (wavelength 380 to 380) is formed. 780 nm) can exhibit low reflectivity, high light-shielding properties, and low gloss, and further, since it is coated with a transparent metal compound as an anti-oxidation film, it can be left in the atmosphere for a long time or in a high temperature and high temperature and high humidity environment. There is no change in the brightness and chromaticity of the film surface caused by oxidation by oxygen and moisture in the film, and it is stable. Further, film oxidation that has been caused by standing in the atmosphere for a long time is suppressed, there is no change in the brightness and chromaticity of the film surface, and the light weight has heat resistance even in a high temperature environment of 270 ° C. or more in the atmosphere. Since a heat-resistant light-shielding film can be realized and the surface has low reflectivity, low glossiness, high light-shielding properties, and blackness, it is useful for various optical members such as a diaphragm and a blade material.
Furthermore, since the heat-resistant light-shielding tape of the present invention is provided with an adhesive layer, if it is affixed to a flexible printed circuit board, it can absorb light leaking from the back surface of an image sensor such as a CCD or CMOS and block its passage. . For this reason, it is possible to suppress the re-incidence of the leaked light to the image sensor and contribute to the stabilization of the image quality.

It is the schematic which shows the cross section of the heat-resistant light-shielding film of this invention which formed the metal light shielding film, the black coating film, and the transparent metal oxide film in the single side | surface of the resin film. It is the schematic which shows the cross section of the heat-resistant light-shielding film of this invention which formed the metal light shielding film, the black coating film, and the transparent metal oxide film on both surfaces of the resin film. It is a schematic diagram of the winding-type sputtering apparatus for forming the metal light-shielding film of this invention, a black coating film, and a transparent metal oxide film on a resin film.

  Hereinafter, the heat-resistant light-shielding multilayer film of the present invention, its production method, and use will be described with reference to the drawings.

1. Heat-resistant and light-shielding multilayer film The heat-resistant and light-shielding multilayer film of the present invention (hereinafter also referred to as heat-resistant and light-shielding film) has a heat resistance of 100 ° C. or higher, and has fine irregularities with an arithmetic average height Ra of 0.2 to 2.2 μm on the surface. The base film is a resin film (A) on which is formed, and the O / Ti atomic ratio in the film is mainly composed of titanium and oxygen as the first layer of the metal light-shielding film (B) on one or both surfaces thereof. A black coating film (C) of the second layer, which is 0.7 to 1.4, and a transparent metal compound film (D) of the third layer are sequentially formed.

The heat-resistant light-shielding multilayer film of the present invention comprises a resin film substrate 1, a metal light-shielding film 2 formed on the surface thereof, a black coating film 3, and a transparent metal compound film 4.
The metal light-shielding film, the black coating film, and the transparent metal compound film may be formed on one side of the resin film base as shown in FIG. 1, but are formed on both sides as shown in FIG. Is preferred. When formed on both surfaces of the resin film substrate, it is more preferable that the composition and thickness of the light-shielding thin film on each surface are the same and that the structure be symmetrical about the film substrate. The thin film formed on the base material gives stress to the base material, which may cause deformation. When a thin film is formed on one side of the substrate, deformation due to film stress may be observed even in a heat-resistant light-shielding film immediately after film formation, but the deformation tends to increase particularly when heated to about 180 ° C. However, the balance of stress is maintained even under the above heating conditions by making the material and film thickness of the light-shielding thin film formed on both surfaces of the base material the same as described above and making the structure symmetrical about the base material. It is easy to realize a heat-resistant light-shielding film without deformation.

The heat-resistant light-shielding multilayer film of the present invention has excellent light-shielding properties, an average optical density at a wavelength of 380 to 780 nm as an index thereof is 4 or more, and a maximum regular reflectance is 0.3% or less. The lower the maximum specular reflectance of a resin film having a large arithmetic average height Ra, the lower the maximum specular reflectance after forming a transparent metal compound film formed on the outermost surface of the film, thereby obtaining extremely low reflectivity. it can. Further, by forming the transparent metal compound film, the L ^* value becomes smaller and the blackness is improved as compared with the color of the film when the metal light shielding film and the black coating film are sequentially formed on the resin film.

  In the heat-resistant light-shielding film of the present invention, a black coating film having titanium and oxygen as main components and an oxygen content in the film of 0.7 to 1.4 is formed on the metal light-shielding film. And is covered with a transparent metal compound film. When the black coating film is on the outermost surface, the black coating film is oxidized by oxygen or moisture being taken into the black coating film due to being left in the atmosphere for a long time or in a high temperature or high temperature and high humidity environment. As a result, the optical constant indicating the optical characteristics of the black coating film changes, the brightness and chromaticity of the black coating film surface change, and the apparent color changes with time. However, since the transparent metal compound film having a metal content in the film having a metal / oxygen atom number ratio of less than 0.8 is formed on the black coating film, the oxidation of the black coating film is suppressed, and the film Surface brightness and chromaticity are less likely to change. This is because the transparent metal compound film is dense and prevents entry of oxygen and moisture in the air into the underlying titanium carbide oxide film. This effect is obtained when the transparent metal compound film is made of a material having high moisture resistance against oxygen and moisture in the atmosphere, such as aluminum oxide, zinc oxide-based metal oxide, silicon dioxide, titanium oxide, and titanium nitride. It will be bigger.

Moreover, the lightness (L ^* value) of the heat-resistant light-shielding multilayer film of this invention is 20-35, and blackness is very high. The lower the regular reflectance, the smaller the L ^* value, the higher the blackness of the film, and it is useful as a diaphragm and blade material for digital cameras and camera-equipped mobile phones that require low regular reflectance and blackness. is there.
The heat-resistant and light-shielding multilayer film of the present invention preferably has a thickness of 10 to 250 μm or less. More preferably, it is 20-150 micrometers, and 30-100 micrometers is still more preferable. If the thickness is less than 10 μm, the handling properties are inferior, so the film tends to have surface defects such as scratches and creases. There is a risk of disappearing.
A gas barrier film may be formed on one side or both sides of the resin film. Oxygen and moisture may be contained in the resin film and may deteriorate due to the action of oxygen on the metal light-shielding film. However, by forming a gas barrier film, the deterioration of the metal light-shielding film can be suppressed. I can do it. As the gas barrier film, a metal oxide film containing nickel as a main component is preferably formed by a sputtering method, and the film thickness is not particularly limited, but is preferably about 5 to 30 nm, for example.
When the heat-resistant light-shielding film of the present invention is left in the atmosphere for 2 weeks, the color difference is less than 1.0, and the change in color is hardly noticed visually. Even if the color difference of the light-shielding film is 1.0 or more, it can be used for a blade material or a diaphragm if there is no problem in characteristics such as light-shielding property and heat resistance.

2. Resin film (A)
The heat-resistant light-shielding film of the present invention uses a resin film having a heat resistance of 100 ° C. or higher as a substrate. The kind of resin is at least one selected from polyimide, polyamideimide, polyphenylene sulfide, polyethylene naphthalate, polyethylene terephthalate, polycarbonate, aramid, polyetheretherketone, or polyethersulfone.

The heat resistance is about 105 ° C. for polyethylene terephthalate and about 140 ° C. for polycarbonate, and can be used in a temperature environment of 105 ° C. and 140 ° C. or less, respectively. Polyethylene naphthalate has a heat resistance of about 200 ° C., and can be used in a temperature environment of 155 to 200 ° C. Further, polyimide, polyamideimide, aramid, polyether ether ketone, polyphenylene sulfide, or polyether sulfone has a heat resistance of 200 ° C. or higher, and can be used in an environment of 200 ° C. or higher. In particular, since polyimide, polyamideimide, and polyetheretherketone are extremely excellent in heat resistant temperature of 300 ° C. or higher, they can be used even in a temperature environment of 300 ° C. or higher. Thus, what is necessary is just to use the material according to the use temperature environment of a heat-resistant light-shielding film for a resin film.
The thickness of the resin film is preferably in the range of 10 to 250 μm, more preferably 20 to 150 μm, and most preferably 30 to 100 μm. A resin film thinner than 10 μm is not preferable because it is difficult to handle due to poor handling properties, and surface defects such as scratches and creases are easily attached to the film. If the resin film is thicker than 250 μm, a plurality of light-shielding blades cannot be mounted on a diaphragm device or a light amount adjusting device that is becoming smaller in size, and desired performance cannot be obtained depending on applications.

Moreover, since the resin film has surface unevenness, if unevenness occurs on the surface of the transparent metal compound film, the regular reflectance of light can be reduced, that is, a matte effect can be brought about, which is preferable as an optical member. It will be a thing. Here, the arithmetic average height is also called arithmetic average roughness, and the reference length is extracted from the roughness curve in the direction of the average line, and the absolute value of the deviation from the average line of the extracted portion to the measurement curve is summed. The average value.
As for the unevenness on the surface of the base material, a predetermined surface unevenness can be formed by nano-imprinting or mat processing using a shot material. In the case of mat processing, mat processing using sand as a shot material is common, but the shot material is not limited to this. Before forming the metal light-shielding film using the resin film as a base material, it is effective to make the surface of the resin film uneven by the above method.

  Moreover, since the resin film is soft, it is easily deformed under the influence of the stress of the film formed on the surface. In order to avoid this, in the heat-resistant light-shielding multilayer film of the present invention, it is effective to form films having the same configuration and the same film thickness on both surfaces of the resin film symmetrically. In other words, after forming a metal light-shielding film with the same composition and the same film thickness on both sides of the resin film, the same composition, a black coating film with the same film thickness on the both surfaces (on the metal light-shielding film), and a black coating film The heat-resistant light-shielding film obtained by forming a transparent metal compound film having the same composition and the same film thickness is preferable because it has less deformation.

3. Metal light shielding film (B)
In the present invention, the metal light-shielding film is a first-layer light-shielding film formed on the resin film (A) as a base material. As the metal material, a material mainly composed of one or more elements selected from titanium, tantalum, tungsten, cobalt, nickel, niobium, iron, zinc, copper, aluminum, and silicon can be used. Among these, metal materials such as Ti, Ni, Cu, Al, or NiTi alloy are preferable.

Further, nitrides, carbides, carbonitrides, carbide oxides, nitride oxides, and carbonitrides of these metals can also be used as the metal light-shielding film. In particular, metal carbide materials such as titanium carbide, tungsten carbide, and molybdenum carbide are preferable because they have excellent oxidation resistance in a high temperature environment and good heat resistance. Among these, titanium carbide is particularly preferable because the surface has a relatively high degree of blackness and excellent low reflectivity, and the effect of blackening the film surface is increased. Further, the titanium carbide oxide film has higher transparency than the titanium carbide film, but can be used as a metal light-shielding film having excellent heat resistance. When the metal light-shielding film is a titanium carbide film or a titanium carbide oxide film, the carbon content in the film is preferably 0.6 or more in terms of the C / Ti atom number ratio. In the case of a titanium carbide oxide film, it is important that the oxygen content in the film be 0.4 or less in terms of the O / Ti atomic ratio in order to exhibit sufficient light shielding properties.
When the metal light-shielding film pays attention to, for example, the adhesion to the resin film substrate, the ratio of the metal binding property and the ion binding property among the bonds of atoms constituting the metal light-shielding film affects the adhesion to the resin film. When the O / Ti atomic ratio of the metal light-shielding film is 0.4 or less, the ratio of ionic bonding among the bonds of atoms constituting the metal light-shielding film is increased. This is preferable because ionic bondability is generated and adhesion is enhanced.
In the metal light-shielding film of the present invention, titanium carbide films having different compositions of carbon content and / or oxygen content are laminated, or the carbon content and / or oxygen content is continuously in the film thickness direction. Even if the titanium carbide oxide film is changed, the average composition of the entire film may be within the composition range defined in the present invention.

  In general, the bond between an organic resin film and an inorganic metal film is weak. The same applies when the light-shielding thin film is formed on the surface of the resin film in the present invention. In order to increase the adhesion of the film, it is effective to increase the film surface temperature during film formation. However, depending on the type of resin film, there are cases where the glass transition point and decomposition temperature are exceeded when the temperature is raised to 130 ° C. or higher, such as PET, so the surface temperature of the resin film during film formation is as low as possible. For example, it is desirable that the temperature be 100 ° C. or lower. In order to form a metal light-shielding film with high adhesion on the surface of a resin film at 100 ° C. or lower, it is indispensable to use a titanium carbide oxide film in which the O / Ti atomic ratio in the film is set to 0.4 or lower. It is.

  The metal light-shielding film in the present invention has a total thickness of 40 nm or more. However, if the film thickness is greater than 250 nm, it takes a long time to form the metal light-shielding film, which increases the manufacturing cost or increases the necessary film forming material and increases the material cost.

4). Black coating film (C)
In the heat resistant light-shielding multilayer film of the present invention, the black coating film of the second layer is composed of Ti and O as main components, and the oxygen content is 0.7 to 1.4 in terms of O / Ti atomic ratio. It is.

The titanium oxide film must have an oxygen content of 0.7 to 1.4 in terms of the O / Ti atomic ratio. When the O / Ti atomic ratio is less than 0.7, the titanium oxide film has a metallic color and is inferior in low reflectivity and blackness. When the O / Ti atomic ratio exceeds 1.4, This is because the transmittance of the film is too high and the light absorption function is poor, and the low reflectivity and blackness are impaired.
Further, the black coating film preferably further contains carbon in the titanium oxide film, and is more preferably a carbonized titanium oxide film having a carbon content of 0.7 or more in terms of the C / Ti atomic ratio. preferable. This is because if the carbon content is 0.7 or more in terms of the C / Ti atomic number ratio, the heat resistance at 300 ° C. is excellent. When the carbon content is less than 0.7 in terms of the C / Ti atomic number ratio, heating to 270 ° C. in the air is not preferable because the film is discolored and the blackness is lowered.
The O / Ti atomic ratio and the C / Ti atomic ratio in the black coating film can be analyzed using, for example, XPS (X-ray photoelectron spectrometer). Since the outermost surface of the film is bonded with a large amount of oxygen, it is removed by sputtering to a depth of several tens of nanometers in vacuum, and if measured thereafter, the O / Ti atomic ratio or C / Ti atomic ratio Can be quantified.

Even with the film composition as described above, the low reflectivity and blackness of the film depend on the film thickness. The film thickness is not particularly limited, but is preferably 50 nm to 250 nm, more preferably 60 to 200 nm, still more preferably 70 to 150 nm. When the film thickness is 50 to 250 nm, light absorption by the film is sufficiently performed, and low reflectivity and blackness can be exhibited.
In the present invention, since the black coating film has the above characteristics, the average parallel light transmittance (Tp) at a wavelength of 380 to 780 nm of the black coating film formed on the optical glass substrate is 13 to 35%. It can be.

  The black coating film may contain elements other than Ti, C, and O to the extent that the above characteristics are not impaired. In general, in a sputtering target used as a raw material for sputtering film formation, a sintering aid is added in order to improve the sintering density of a sintered body as the material. Specifically, elements such as Fe, Ni, Co, Zn, Cu, Mn, In, Sn, Nb, and Ta are added to the sintered body target as a sintering aid, and the added element is a black coating. It will also be included in the coating. Thus, even if the above-mentioned element is contained in the black coating film, the characteristics of the black coating film may be impaired.

5. Transparent metal compound film (D)
In the present invention, the transparent metal compound film is formed as a third-layer antioxidant film on the black coating film, and is one or more selected from aluminum, titanium, silicon, zinc, indium, gallium, tin, and magnesium. These elements are oxides, nitride oxides, carbonized oxides, and carbonitride oxides. Further, the transparent metal compound film formed on the optical glass substrate has a film thickness necessary for the average parallel light transmittance at a wavelength of 380 to 780 nm to be 70% or more and the average regular reflectance to be 20% or less. .

The material of the transparent metal compound film must contain one or more elements selected from aluminum, titanium, silicon, zinc, indium, gallium, tin, and magnesium and oxygen. Furthermore, nitrogen and carbon may be included. Specifically, aluminum oxide (Al ₂ O ₃ ), titanium oxide (TiO ₂ ), silicon oxide (SiO ₂ ), indium oxide (In ₂ O ₃ ) -tin oxide (SnO ₂ ) -based oxide, indium oxide ( In ₂ O ₃ ) -titanium oxide (TiO ₂ ) -based oxide, zinc oxide (ZnO), oxide film such as zinc oxide-based oxide to which tin, aluminum, gallium, magnesium, or the like is added, titanium oxynitride ( TiON), silicon oxynitride (SiON), aluminum oxynitride (AlON), carbonized titanium oxide (TiCO), carbonitrided titanium oxide (TiCON), nitrided oxide films, carbonized oxide films, carbonitrided oxide films, etc. .
As with the resin film, the transparent metal compound film may be selected from an appropriate material according to the use temperature environment. For example, if the use temperature environment is 300 ° C. or higher, aluminum oxide, titanium oxide, silicon oxide, etc. If it is 280 ° C. or lower, a zinc oxide-based oxide or an indium oxide-tin oxide-based oxide may be used.
In the present invention, the transparent metal compound film is a dense film, and is composed of a component having low permeability to gas such as moisture and oxygen, so that oxygen and moisture in the atmosphere are black coating films such as titanium carbide oxide films. It has an action of preventing intrusion into the inside and preventing oxidation of the black coating film.

  The metal content in the film must be less than 0.8 in the metal / oxygen number ratio. When the metal / oxygen atomic ratio is 0.8 or more as the content of the metal component, the metal compound film is colored, the transparency is impaired and light absorption occurs, and on the optical glass (Corning Corporation: 7059). When the film is formed, the parallel light transmittance at a wavelength of 380 to 780 nm of the transparent metal compound film is less than 70%, and high transmittance cannot be obtained. If it is not highly permeable, the blackness of the underlying black coating film is not reflected, and the transparent metal compound film itself is colored, which is not preferable. In addition, since the metal component in the film increases, the regular reflectance on the film surface increases, and the average regular reflectance exceeds 20%. If it does so, since the average regular reflectance of a heat-resistant light-shielding film will be 0.3% or more, it is unpreferable. Furthermore, oxidation of the metal component under high temperature environment and high temperature and high humidity becomes remarkable, the parallel light transmittance and regular reflectance change, and the film is discolored.

If the metal component content is less than 0.8, the average parallel light transmittance at a wavelength of 380 to 780 nm can be 70% or more, and the average regular reflectance can be 20% or less. Aluminum oxide Excellent heat resistance under high temperature environment and high humidity such as titanium oxide, silicon oxide, zinc oxide oxide, indium oxide-tin oxide oxide, or aluminum nitride. A light-shielding film can be obtained.
Further, by forming such a transparent metal compound film on the black coating film as the second layer, an antireflection effect due to the light confinement effect is exhibited, and a metal light-shielding film and a black coating film are sequentially formed. It is possible to reduce the average regular reflectance on the surface of the heat-resistant light-shielding film and improve the blackness of the film more than the heat-resistant light-shielding film.
In addition, the transparent metal compound film is not a single film but may be a laminated film of two or more kinds of transparent metal compound films as long as the characteristics of the heat-resistant light-shielding film can be satisfied.

6). Manufacturing method of heat-resistant light-shielding film The manufacturing method of the heat-resistant light-shielding film of the present invention is as follows. Sputtering is performed using a metal light-shielding film target in a gas atmosphere to form a metal light-shielding film (B) on the resin film (A), and then under a deposition gas pressure of 1.5 Pa or more in an inert gas atmosphere. Then, sputtering is performed using a target for forming a black coating film, and the O / Ti atomic ratio in the film is mainly 0.7 to 1. on the metal light-shielding film (B) with titanium, oxygen, and carbon as main components. After forming the black coating film (C) which is 4,
Sputtering using a transparent metal compound (D) forming target in an inert gas atmosphere, an oxide of one or more elements selected from aluminum, titanium, silicon, zinc, indium, gallium, tin, and magnesium, A transparent metal compound (D) which is a nitride oxide, a carbide oxide, or a carbon nitride oxide and has a metal content in the film of less than 0.8 as a metal / oxygen atom ratio is characterized.

The metal light-shielding film of the first layer in the present invention is not particularly limited depending on the production method, and vacuum deposition method, ion beam assisted deposition method, gas cluster ion beam assisted deposition method, ion plating method, ion beam sputtering method, magnetron sputtering. Known methods such as a sputtering method, a bias sputtering method, an ECR (Electron Cyclotron Resonance) sputtering method, a radio frequency (RF) sputtering method, a thermal CVD (Chemical Vapor Deposition) method, a plasma CVD method, and a photo CVD method can be appropriately employed. . Especially, it is preferable to manufacture by a sputtering method. This is because it can be formed not only uniformly on a large-area substrate but also with high adhesion to the substrate by being produced by the sputtering method.
In the heat-resistant light-shielding film of the present invention, the metal light-shielding film is preferably formed on a resin film substrate by, for example, a direct current magnetron sputtering method in an argon atmosphere. The discharge method may be high-frequency discharge, but direct current discharge enables high-speed film formation.
The production apparatus by the sputtering method is not particularly limited. For example, as shown in FIG. 3, a roll-shaped resin film substrate 1 is set on an unwinding roll 12A, and the film forming chamber is vacuumed by a vacuum pump such as a turbo molecular pump. After evacuating the inside of the tank, use a winding type sputtering apparatus in which the film 1 unloaded from the unwinding roll 12A passes through the surface of the can roll 15 and is wound up by the winding roll 12B. Can do. A magnetron cathode 13A is installed on the opposite side of the surface of the can roll 15, and a target 14A as a film raw material is attached to the cathode 13A. In addition, the film conveyance part comprised by the unwinding roll 12A, the can roll 15, the winding roll 12B, etc. is isolated from the magnetron cathode 13A by the partition 16.

  As the target, for example, a target obtained by processing a sintered body mainly composed of titanium carbide or titanium carbide oxide is used. The composition is not particularly limited, but the same composition as that of the metal light-shielding film initially formed on the substrate is preferable. In a sintered body of a sputtering target used as a raw material for sputtering film formation, a sintering aid is often added in order to improve the sintering density. In the sintered compact target used in the present invention, elements such as Fe, Ni, Co, Zn, Cu, Mn, In, Sn, Nb, and Ta are sintered so long as the characteristics of the present invention are not impaired. It can be added as an auxiliary agent.

In sputtering film formation, the gas pressure varies depending on the type of apparatus and the like, and thus cannot be specified unconditionally. However, Ar gas or 0.05% at a sputtering gas pressure of 1 Pa or less, preferably 0.2 to 0.8 Pa is preferable. A method of using Ar gas mixed with O ₂ as a sputtering gas can be employed.
Hereinafter, when a resin film is used as the substrate and a metal film is used as the metal light-shielding film, the sputtered particles reaching the substrate have high energy, so that a crystalline metal film is formed on the resin film substrate. Strong adhesion is developed between the metal film and the resin film. When the gas pressure at the time of film formation is less than 0.2 Pa, since the gas pressure is low, the argon plasma in the sputtering method becomes unstable and the film quality deteriorates. If it is less than 0.2 Pa, the mechanism for resputtering the metal film on which the recoil argon particles are deposited on the substrate becomes strong, and the formation of a dense metal film is likely to be hindered. Also, when the gas pressure at the time of film formation exceeds 0.8 Pa, the energy of the sputtered particles reaching the substrate is low, so that the crystal growth is difficult, the metal film grains become coarse, and the film quality is high and the crystallinity is high. Since it disappears, the adhesive force with the resin film substrate becomes weak, and the film is peeled off. Such a film cannot be used as a metal light-shielding film for heat resistance. As a result, a metal light-shielding film having excellent crystallinity can be stably formed by using pure Ar gas or Ar gas mixed with a small amount of O ₂ (for example, within 0.05%) as a sputtering gas. If 0.1% or more of O ₂ is mixed, the crystallinity of the thin film may deteriorate, which is not preferable.

The resin film surface temperature during film formation affects the crystallinity of the metal film. The higher the film surface temperature during film formation, the easier the crystal alignment of the sputtered particles occurs and the better the crystallinity. However, the heating temperature of the resin film is also limited, and the surface temperature of the polyimide film having the most excellent heat resistance needs to be 400 ° C. or lower. Depending on the type of resin film, when the temperature is raised to 130 ° C. or higher, the glass transition point or decomposition temperature may be exceeded. For example, in PET, the film surface temperature during film formation is as low as possible, for example, 100 ° C. The following is desirable. In view of the manufacturing cost, considering the heating time and the heat energy for heating, it is effective to reduce the cost to form the film at as low a temperature as possible. The film surface temperature during film formation is preferably 90 ° C. or lower, more preferably 85 ° C. or lower.
Further, the resin film substrate is naturally heated from plasma during film formation. The surface temperature of the resin film substrate during film formation is controlled by adjusting the gas pressure, the input power to the target, and the film transport speed, so that the surface temperature of the resin film substrate is controlled by the thermal electrons incident on the substrate and the thermal radiation from the plasma. Can be easily maintained. The lower the gas pressure, the higher the input power, and the slower the film transport speed, the higher the heating effect by natural heating from the plasma. Even in the case of a sputtering apparatus in which a resin film is brought into contact with a cooling can during film formation, the temperature of the film surface is much higher than the cooling can temperature due to the effect of natural heating.
However, in the sputtering apparatus as shown in FIG. 3 in which the target is installed at a position facing the can roll, the film 1 is conveyed while being cooled by the can roll 15. Since the temperature of the film surface due to natural heating also greatly depends on the temperature of the can roll 15, if the effect of natural heating at the time of film formation is used, the temperature of the cooling can is increased as much as possible to lower the conveyance speed. It is effective. The film thickness of the metal film is controlled by the film conveyance speed at the time of film formation and the power input to the target, and becomes thicker as the conveyance speed is slower and the power input to the target is larger.
As described above, the case where the metal film is formed as the metal light-shielding film has been described. However, the same conditions can be adopted when the black coating film is formed.

In FIG. 3, the film 1 on which the metal light-shielding film is formed as described above continues to pass through the surface of the can roll 15, and the target 14 </ b> B that is the raw material of the film installed on the magnetron cathode 13 </ b> B installed on the opposite side of the surface. As a result, a black coating film is formed.
Usually, sputtering film formation is often performed at a sputtering gas pressure of 0.2 to 0.8 Pa. Under such conditions, the film surface becomes relatively flat. The black coating film of the present invention is formed by sputtering using a titanium oxide, a mixture of titanium oxide and titanium carbide, or a sintered carbon target of titanium carbide oxide at a high sputtering gas pressure of 1.5 Pa or more. Therefore, a protrusion is formed on the film surface, and a high quality titanium oxide film or a titanium carbide oxide film having the above composition and structure is obtained.
Using a sintered body target made of titanium oxide and titanium carbide, or a sintered body target made of titanium carbide oxide, or a sintered body target made of titanium oxide, titanium carbide, or titanium carbide oxide, sputtering film formation was similarly performed. , O as the main component, the oxygen content is 0.7 to 1.4 in terms of O / Ti atomic ratio, and further contains carbon, and the content is 0.7 or more in terms of C / Ti atomic ratio. In addition, a black coating film having fine protrusions on the film surface can be obtained. In both cases, it is possible to perform film formation by mixing O ₂ gas with Ar gas at the time of film formation, and performing film formation by introducing a larger amount of oxygen into the film.

In the present invention, it is also possible to form a black coating film by using only an inert gas mainly containing argon or helium without supplying oxygen gas as a film forming gas. In this case, oxygen contained in the sintered body target and / or oxygen in the residual gas in the sputtering film forming chamber is effectively used as oxygen in the film. The oxygen contained in the sintered compact target and the oxygen in the residual gas in the sputtering film forming chamber are very small. When the film forming gas pressure is increased, the ratio of taking oxygen in the film forming chamber into the film increases. When the oxygen contained in the sintered body target and the oxygen in the residual gas in the sputtering film forming chamber are too small, the normal sputtering film forming of 0.2 to 0.8 Pa does not contain enough oxygen in the film. In this case, by setting the film forming gas pressure to 1.5 Pa or more, it is possible to obtain a black coating film by sufficiently containing oxygen.
A film forming method that uses oxygen contained in the sintered compact target and oxygen in the residual gas in the sputtering film forming chamber is an extremely effective method for forming a uniform color over a large area. In a normal method of forming a film at a normal gas pressure by supplying oxygen gas, if the supply of oxygen gas is not uniform, in the case of large-area film formation, it is caused by unevenness of oxygen content in the film. And uneven color. However, the film formation method that uses oxygen contained in the sintered compact target and oxygen in the residual gas in the sputtering film formation chamber has oxygen uniformly on the film formation surface. Uneven taste is less likely to occur.

In the present invention, after the black coating film (C) is formed as described above, the transparent metal compound film (D) of the third layer is formed.
That is, one or more elements selected from aluminum, titanium, silicon, zinc, indium, gallium, tin, and magnesium are sputtered using a transparent metal compound film (D) target in an inert gas atmosphere. And forming a transparent metal compound film (D) in which the metal content in the film is less than 0.8 as a metal / oxygen atom number ratio.

The transparent metal compound film (D) can employ the same conditions as those for forming the metal light-shielding film and the black coating film.
In FIG. 3, the film 1 on which the metal light-shielding film and the black coating film are formed as described above passes through the surface of the can roll 15, and the film installed on the magnetron cathode 13 </ b> C installed on the opposite side of the surface. A transparent metal compound film is formed by the target 14C as a raw material.

The transparent metal compound film (D) in the present invention is an oxide, nitride oxide, carbide oxide or carbonitride of one or more elements selected from aluminum, titanium, silicon, zinc, indium, gallium, tin and magnesium. It is an oxide, and the metal content is less than 0.8 in terms of the metal / oxygen atom ratio. Therefore, any one of a metal target, a metal oxide target, a metal carbide target, or a metal nitride target containing one or more elements selected from aluminum, titanium, silicon, zinc, indium, gallium, tin, and magnesium is used. Then, oxygen gas and / or nitrogen gas is introduced into argon gas, and sputtering is performed at a film forming gas pressure of 0.2 to 0.8 Pa.
In the present invention, the transparent metal compound film can also be formed by using only an inert gas mainly containing argon or helium without supplying oxygen gas at all as a film forming gas. In this case, oxygen contained in the sintered body target and / or oxygen in the residual gas in the sputtering film forming chamber is effectively used as oxygen in the film. The oxygen contained in the sintered compact target and the oxygen in the residual gas in the sputtering film forming chamber are very small. When the film forming gas pressure is increased, the ratio of taking oxygen in the film forming chamber into the film increases. When the oxygen contained in the sintered body target and the oxygen in the residual gas in the sputtering film forming chamber are too small, the normal sputtering film forming of 0.2 to 0.8 Pa does not contain enough oxygen in the film. In this case, by setting the film forming gas pressure to 1.5 Pa or more, it is possible to obtain a transparent metal compound film by sufficiently containing oxygen.

7). Applications of heat-resistant and light-shielding multilayer film The heat-resistant and light-shielding multilayer film of the present invention is stamped into a specific shape so that end face cracks do not occur, and fixed apertures for digital cameras and digital video cameras, mechanical shutter blades and certain shutters. It can be used as a heat-resistant light-shielding tape that shields incident light from a diaphragm (iris) through which only the amount of light passes, a diaphragm blade of a light amount adjusting diaphragm device (auto iris) of a liquid crystal projector, and a back surface of an image sensor such as a CCD or CMOS.

In the light quantity adjusting diaphragm device of a liquid crystal projector, heating by irradiation with lamp light is remarkable. Therefore, a light amount adjusting diaphragm device equipped with diaphragm blades that are manufactured by processing the heat-resistant and light-shielding multilayer film of the present invention and that has excellent heat resistance and light-shielding properties is useful. In addition, when a fixed aperture or a mechanical shutter is assembled in the reflow process to manufacture the lens unit, if the fixed aperture or shutter blade obtained by processing the heat-resistant light-shielding multilayer film of the present invention is used, This is very useful because the characteristics do not change even under the heating environment. Furthermore, the fixed aperture in the lens unit of the in-vehicle video camera monitor is remarkably heated by sunlight in summer, and for the same reason, it is useful to apply a fixed aperture made from the heat-resistant light-shielding multilayer film of the present invention. .
In the heat-resistant light-shielding multilayer film of the present invention, a heat-resistant light-shielding tape or sheet can be obtained by providing an adhesive layer on one or both surfaces of the light-shielding plate. The pressure-sensitive adhesive for forming the pressure-sensitive adhesive layer is not particularly limited, and a pressure-sensitive adhesive suitable for the use environment such as temperature and humidity can be selected from those conventionally used for pressure-sensitive adhesive sheets.
As a general adhesive, an acrylic adhesive, a rubber adhesive, a polyurethane adhesive, a polyester adhesive, a silicone adhesive, or the like can be used. In particular, when a lens unit of a cellular phone is assembled in a reflow process, heat resistance is required, and therefore, an acrylic adhesive or a silicone adhesive having high heat resistance is preferable.
Moreover, as a method for forming the adhesive layer on the heat-resistant light-shielding multilayer film, for example, a conventionally known method such as a bar coating method, a roll coating method, a gravure coating method, an air doctor coating method or a doctor blade coating method can be used.
Although the thickness in particular of an adhesion layer is not restrict | limited, 2-60 micrometers is preferable. Within this range, even small and thin digital cameras and camera-equipped mobile phones can be easily attached and are not easily dropped.
Smaller and thinner digital cameras and camera-equipped mobile phones use smaller and thinner components. As described above, when the imaging device such as a CCD or CMOS or the FPC on which the imaging device is mounted is thin, the leakage light that is transmitted through the FPC and incident from the back surface of the imaging device is not only leakage light from the front surface of the imaging device. Become more. The leakage light from the back surface of the imaging element causes the FPC wiring circuit to appear in the imaging area, resulting in degradation of imaging quality. Since the heat-resistant light-shielding tape provided with an adhesive layer on one side or both sides of the heat-resistant and light-shielding multilayer film of the present invention can be attached to the periphery on the back side of an image sensor such as a CCD or CMOS by the adhesive layer. This is useful for shielding light incident on the back surface of the image sensor.

  Next, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. The heat resistant light-shielding multilayer film was produced and evaluated by the following method.

(Production method of heat-resistant light-shielding multilayer film)
The metal light-shielding film was formed on the resin film substrate using the winding type sputtering apparatus shown in FIG. First, a metal light-shielding film forming target 14A serving as a film raw material was attached to a cathode 14B of an apparatus in which a magnetron cathode was installed on the opposite side of the surface of the can roll 15. A film transport unit composed of the unwinding roll 12A, the can roll 15, the winding roll 12B and the like is separated from the magnetron cathode by a partition wall. Next, the roll-shaped resin film base material 1 was set to the unwinding roll 12A.
The resin film substrate whose surface was adjusted to a predetermined arithmetic average height Ra by sandblasting was sufficiently dried by sputtering and closely transported to the surface of a can roll heated to a temperature of 70 ° C. in a vacuum.
Next, the inside of the vacuum chamber is evacuated by a vacuum pump such as a turbo molecular pump, and then discharged between the can roll 15 and the cathode to form a metal light shielding film while closely transporting the resin film substrate 1 to the can roll surface. Went. At this time, the preset temperature of the can roll was 70 ° C., and the distance between the target and the substrate was 75 mm. The ultimate vacuum in the vacuum chamber before film formation was 4 × 10 ⁻⁴ Pa or less.
The metal light shielding film as the first layer was formed as follows. Pure argon gas (purity 99.999%) was introduced into the vacuum chamber, and the film forming gas pressure was adjusted to 0.2 to 0.8 Pa. Film formation was performed by applying a DC power density of 4 to 18 W / cm ² (DC input power per unit area on the sputtering surface of the target) to the target. The film thickness of the metal light-shielding film was controlled by controlling the film conveyance speed during film formation and the input power to the target. The resin film substrate 1 unloaded from the unwinding roll 12A passed through the surface of the can roll 15 and was wound up by the winding roll 12B.
Next, for the black coating film as the second layer film, the black coating film forming target 14B is placed on the cathode 13B, the inside of the vacuum chamber is evacuated, and the ultimate degree of vacuum is 4 × 10 ^−4. It adjusted to Pa or less. Pure argon gas (purity 99.999%) was introduced into the vacuum chamber, and the film forming gas pressure was adjusted to 1.5 to 12.0 Pa. The target 14B was subjected to film formation by applying a DC power density of 2 to 12 W / cm 2, and the resin film substrate 1 was wound up by a winding roll 12B.
Further, for the transparent metal compound film as the third layer film, first, the resin film on which the metal light-shielding film and the black coating film are formed is set on the unwinding roll, and the target 14C for forming the transparent metal compound film is used as the cathode. It was installed at 13C, the inside of the vacuum chamber was evacuated, and the ultimate vacuum was adjusted to 3 × 10 ⁻⁴ Pa or less. Next, pure argon gas (purity 99.999%) and / or pure oxygen gas (purity 99.999%) is introduced into the cathode in the vacuum chamber, and the film forming gas pressure is reduced to 0.1 to 1.0 Pa. It was adjusted. A DC power density of 4 to 17 W / cm ² is input to the target 14C, a transparent metal compound film having a predetermined thickness is formed on the black coating film, and the resin film substrate 1 is wound on the winding roll 12B. The heat-resistant light-shielding film in which the metal light-shielding film, the black coating film, and the transparent metal compound film were formed on one side of the resin film was produced.
When making a heat-resistant light-shielding film with a metal light-shielding film, black coating film, and transparent metal compound film formed on both sides of the resin film, the metal light-shielding film, black coating film, and transparent The heat-resistant light-shielding film on which the metal compound film is formed is set on an unwinding roll, and the resin film is set so that the resin film surface on which the film is not formed on the cathode side faces the can roll surface. After that, the metal film, the black coating film, and the transparent metal compound film are formed from the vacuum exhaust in the same manner as described above, so that the metal light shielding film, the black coating film, and the transparent metal compound film are formed on both sides of the resin film A heat-resistant light-shielding film can be produced.

(Average optical density, average parallel light transmittance, average regular reflectance)
About the obtained heat-resistant light-shielding multilayer film, the spectrophotometer (product made from JASCO: V-570) was used, and the light-shielding property, the transmittance | permeability, and the regular reflectance of wavelength 380nm -780nm were measured.
The optical density (denoted as OD) was calculated according to the following equation using the transmittance (T) measured with a spectrophotometer. The transmittance is a numerical value including a resin film substrate and an optical glass substrate.
Optical density (OD) = Log (1 / T)
In order to obtain complete light shielding properties, the average optical density at a wavelength of 380 to 780 nm needs to be 4 or more.
The parallel light transmittance is the ratio of the transmitted light parallel to the incident light with respect to the incident light, and the regular reflectance is reflected from the surface at an angle equal to the incident angle of the incident light according to the law of reflection. The incident light is measured at an incident angle of 5 °. If the average parallel light transmittance (including the optical glass substrate) obtained from the measured parallel light transmittance is 70% or more, it is considered good, and the average regular reflectance obtained from the regular reflectance is 0.3% or less. If there was, it was considered good.
The average optical density, the average parallel light transmittance, and the average regular reflectance are arithmetic average values for the wavelengths of 380 to 780 nm.

(Arithmetic mean height Ra)
The arithmetic average height Ra of the resin film substrate was measured with a surface roughness meter (manufactured by Tokyo Seimitsu Co., Ltd .: Surfcom 570A).
(Membrane composition)
The composition of the obtained film (C / Me atomic ratio, O / Me atomic ratio: Me is a metal component) was quantitatively analyzed by XPS (manufactured by VG Scientific: ESCALAB220i-XL). In the quantitative analysis, the surface of the film was sputter-etched at 20 to 30 nm, and then the composition analysis inside the film was performed.
(Lightness of film surface (L ^* ), chromaticity indicating hue and saturation (a *, b *))
The lightness (L ^* ) and chromaticity (a ^* , b ^* ) values indicating the hue and saturation of the film and heat-resistant light-shielding film were standardized by the CIE (International Commission on Illumination), and JIS (JISZ8729) was also used in Japan. In accordance with the L ^* a ^* b ^* color system measurement standardized in (1)), measurement was performed with a color meter (manufactured by BYK-Gardner GmbH: trade name Spectroguide) at a light source D65 and a viewing angle of 10 °.
(Antioxidation)
Immediately after film formation, the surface color, L * value, a ^* value, and b ^* value were measured, and two weeks later, the L ^* value, a ^* value, and b ^* value were measured again. The color difference (ΔE ^* ab) indicating the change was evaluated. The color difference was calculated using the following formula. If the color difference was less than 1.0, the color difference was good, and if it was more than that, it was unsuitable.
ΔE ^* ab = ((ΔL ^* ) ² + (Δa ^* ) ² + (Δb ^* ) ² ) ^(1/2)
(Heat-resistant)
About heat resistance of a heat-resistant light-shielding film, it heat-processes on conditions (100 degreeC, 200 degreeC, and 270 degreeC for 30 minutes) in oven (the product made from Advantech: model number DRD320DA), average optical density, average regular reflectance, Checked the color difference. The average optical density and the average regular reflectance after the heat test are not changed if the difference is 0.2 or less in the average optical density and 0.1% or less in the average regular reflectance as compared with that before the heat test. did. A color difference of less than 1.0 was considered good.

(Durability under high temperature and high humidity)
Regarding the durability of the heat-resistant light-shielding film in a high-temperature and high-humidity environment, it was treated at a temperature of 85 ° C. and a humidity of 85% RH for 500 hours, and the average optical density, average regular reflectance, and presence / absence of a color difference were checked.
The average optical density and average regular reflectance after the test were not changed if the difference was 0.2 or less in average optical density and 0.1% or less in the average regular reflectance compared to before testing. A color difference of less than 1.0 was considered good.
(Adhesion)
The adhesion of the film to the film substrate was evaluated after a heat resistance test and a high temperature and high humidity test, and evaluated based on JIS C0021 (cross cut test). Evaluation was good when there was no film peeling, and the film with film peeling was inappropriate.

Example 1
Using a titanium carbide (TiC) target on the surface of a 38 μm thick polyimide film with an arithmetic average height (Ra) of 0.5 μm on both surfaces of the film by sandblasting, the film forming gas pressure is set to 0.3 Pa. Then, a titanium carbide film (film thickness: 120 nm) was formed as the first layer metal light-shielding film. Similarly, a sample in which a titanium carbide (TiC) film was formed on an optical glass (Corning Corp .: 7059) was also produced. As a result of analyzing the composition of the titanium carbide (TiC) film formed on the optical glass by XPS (X-ray photoelectron emission analyzer), the carbon content in the film is 0.99 as the C / Ti atomic ratio, and the oxygen content is The O / Ti atomic ratio was 0.05.
Next, on the titanium carbide (TiC) film formed on the polyimide film surface, the film forming gas pressure is adjusted to 6.0 Pa using a titanium carbide (TiC) target, and the second layer black coating film, A titanium carbide oxide (TiCO) film was formed to a thickness of 105 nm. The brightness (L ^* ) of the titanium carbide (TiC) film and the titanium carbide oxide (TiCO) film laminated film formed on the polyimide film was measured and found to be 36.
Similarly, a sample in which a titanium carbide oxide (TiCO) film was formed on optical glass (Corning Corp .: 7059) was also produced. As a result of analyzing the composition of the titanium carbide oxide (TiCO) film formed on the optical glass by XPS (X-ray photoelectron emission analyzer), the oxygen content in the film was 0.89 as the O / Ti atomic ratio.
Further, pure argon is formed on a laminated film of a titanium carbide (TiC) film and a titanium carbide oxide (TiCO) film sequentially formed on a polyimide film by using a zinc oxide (ZnO) -aluminum oxide (Al ₂ O ₃ ) target. A gas was introduced to form a third transparent metal compound film, that is, a zinc oxide (ZnO) -aluminum oxide (Al ₂ O ₃ ) film having a film thickness of 15 nm at a film forming gas pressure of 0.3 Pa. A film was prepared. Further, a sample in which a zinc oxide (ZnO) -aluminum oxide (Al ₂ O ₃ ) film was similarly formed on an optical glass (Corning Corp .: 7059) was also produced. As a result of analyzing the composition of the zinc oxide (ZnO) -aluminum oxide (Al ₂ O ₃ ) film formed on the optical glass by XPS (X-ray photoelectron emission analyzer), the oxygen content in the film is a metal component (Zn + Al) / The O atom number ratio was 0.4. The zinc oxide (ZnO) -aluminum oxide (Al ₂ O ₃ ) film formed on the optical glass substrate has a high light transmittance such that the average parallel light transmittance at a wavelength of 380 to 780 nm is 82% and the average regular reflectance is 17%. It was a membrane.
The average optical density at a wavelength of 380 to 780 nm of a heat-resistant light-shielding film comprising a titanium carbide film, a titanium carbide oxide film, and a zinc oxide (ZnO) -aluminum oxide (Al ₂ O ₃ ) film formed on a polyimide film is 4 or more and an average positive The reflectance was 0.15%, the lightness (L ^* ) of the film surface was 32, and the blackness was increased by forming a zinc oxide (ZnO) -aluminum oxide (Al ₂ O ₃ ) film.
Further, after the preparation, the sample was left in the atmosphere for 2 weeks, but the color difference (ΔE ^* ab) representing the antioxidant property was calculated to be 0.3, and the color change was invisible to the naked eye.
It was left in the atmosphere for 2 weeks, and it was heated at 100 ° C, 200 ° C, 270 ° C for 30 minutes and treated at a temperature of 85 ° C and a humidity of 85% RH for 500 hours, but there was no change in the average optical density and average regular reflectance. The color difference (ΔE ^* ab) was also 0.1 to 0.4, which was not visible. In the heat resistance test and the adhesion test after the high temperature and high humidity test, the film was not peeled off. Table 1-1 shows the configuration of the heat-resistant light-shielding multilayer film, and Table 1-2 shows the characteristics.
Therefore, the produced heat-resistant light-shielding multilayer film has a complete light-shielding property, low regular reflectance, and extremely high blackness, so it can be used for camera module apertures for camera-equipped mobile phones and shutter blade materials for digital cameras. Use is useful.

(Example 2)
Except for changing the mat processing conditions and changing the arithmetic average height Ra of the polyimide film to 0.20 μm, the types, film thicknesses, and compositions of the metal light-shielding film, black coating film and transparent metal compound were the same as in Example 1. Thus, a heat-resistant and light-shielding multilayer film was produced. As shown in Table 1, the characteristics of the heat-resistant and light-shielding multilayer film were found to be equivalent to those of Example 1.
The average optical density at a wavelength of 380 to 780 nm of the heat-resistant light-shielding multilayer film is 4 or more, the average regular reflectance is 0.20%, the lightness (L ^* ) of the film surface is 33, and zinc oxide (ZnO) -aluminum oxide ( The blackness was increased by forming an (Al ₂ O ₃ ) film.
Further, after the production, the sample was left in the atmosphere for 2 weeks, but the color difference (ΔE ^* ab) was calculated to be 0.3, and the color change was invisible to the naked eye.
It was left in the atmosphere for 2 weeks, and it was heated at 100 ° C, 200 ° C, 270 ° C for 30 minutes and treated at a temperature of 85 ° C and a humidity of 85% RH for 500 hours, but there was no change in the average optical density and average regular reflectance. The color difference (ΔE ^* ab) was also 0.1 to 0.4, which was not visible. In the heat resistance test and the adhesion test after the high temperature and high humidity test, the film was not peeled off. Table 1-2 summarizes the characteristics of the heat-resistant and light-shielding multilayer film.
Therefore, the produced heat-resistant light-shielding multilayer film has a complete light-shielding property, low regular reflectance, and extremely high blackness, so it can be used for camera module apertures for camera-equipped mobile phones and shutter blade materials for digital cameras. Use is useful.

(Example 3)
Except for changing the mat processing conditions and changing the arithmetic average height Ra of the polyimide film to 2.2 μm, the type, film thickness, and composition of the metal light-shielding film, black coating film, and transparent metal compound were the same as in Example 1. Thus, a heat-resistant and light-shielding multilayer film was produced.
The average optical density at a wavelength of 380 to 780 nm of the heat resistant light-shielding multilayer film is 4 or more, the average regular reflectance is 0.10%, the lightness (L ^* ) of the film surface is 24, and zinc oxide (ZnO) -aluminum oxide ( The blackness was increased by forming an (Al ₂ O ₃ ) film. Further, after the production, the sample was left in the atmosphere for 2 weeks, but the color difference (ΔE ^* ab) was calculated to be 0.3, and the color change was invisible to the naked eye.
It was left in the atmosphere for 2 weeks, and it was heated at 100 ° C, 200 ° C, 270 ° C for 30 minutes and treated at a temperature of 85 ° C and a humidity of 85% RH for 500 hours, but there was no change in the average optical density and average regular reflectance. The color difference (ΔE ^* ab) was also 0.1 to 0.4, which was not visible. In the heat resistance test and the adhesion test after the high temperature and high humidity test, the film was not peeled off. Table 1-2 summarizes the characteristics of the heat-resistant and light-shielding multilayer film.
Therefore, the produced heat-resistant light-shielding multilayer film has a complete light-shielding property, low regular reflectance, and extremely high blackness, so it can be used for camera module apertures for camera-equipped mobile phones and shutter blade materials for digital cameras. Use is useful.

(Comparative Example 1)
Except for changing the mat processing conditions and changing the arithmetic average height Ra of the polyimide film to 0.10 μm, the types, film thicknesses and compositions of the metal shading film, black coating film and transparent metal compound were the same as in Example 1. Thus, a heat-resistant light-shielding film was produced.
The average optical density of the heat-resistant light-shielding film at a wavelength of 380 to 780 nm is 4 or more, the average regular reflectance is 0.90%, the lightness (L ^* ) of the film surface is 40, and zinc oxide (ZnO) -aluminum oxide (Al _{Even when the 2} O ₃ ) film was formed, the blackness did not change.
In addition, after the production, the sample was left in the atmosphere for 2 weeks, but the color difference (ΔE ^* ab) was calculated to be 0.4, and the color change was invisible to the naked eye.
It was left in the atmosphere for 2 weeks, and it was heated at 100 ° C, 200 ° C, 270 ° C for 30 minutes and treated at a temperature of 85 ° C and a humidity of 85% RH for 500 hours, but there was no change in the average optical density and average regular reflectance. The color difference (ΔE ^* ab) was also 0.1 to 0.4, which was not visible. In the heat resistance test and the adhesion test after the high temperature and high humidity test, the film was not peeled off. Table 1-2 summarizes the characteristics of the heat-resistant light-shielding film.
Therefore, since the produced heat-resistant light-shielding film has a very high regular reflectance and lightness (L ^* ), it cannot be used for an aperture for a camera module for a camera-equipped mobile phone or a shutter blade material for a digital camera.

(Comparative Example 2)
Except for changing the mat processing conditions and changing the arithmetic average height Ra of the polyimide film to 2.3 μm, the types, film thicknesses and compositions of the metal shading film, black coating film and transparent metal compound were the same as in Example 1. Thus, a heat-resistant light-shielding film was produced.
The average optical density at a wavelength of 380 to 780 nm of the heat-resistant light-shielding film is 4 or more, the average regular reflectance is 0.10%, the lightness (L ^* ) of the film surface is 22, and zinc oxide (ZnO) -aluminum oxide (Al _The degree of blackness was increased by forming a ₂ O ₃ ) film.
In addition, after the preparation, the sample was left in the atmosphere for 2 weeks, but the color difference (ΔE ^* ab) was calculated to be 0.4, and the color change was invisible to the naked eye.
It was left in the atmosphere for 2 weeks, and it was heated at 100 ° C, 200 ° C, 270 ° C for 30 minutes and treated at a temperature of 85 ° C and a humidity of 85% RH for 500 hours, but there was no change in the average optical density and average regular reflectance. The color difference (ΔE ^* ab) was also 0.1 to 0.4, which was not visible. In the heat resistance test and the adhesion test after the high temperature and high humidity test, the film was not peeled off. Table 1-2 summarizes the characteristics of the heat-resistant light-shielding film.
However, since the arithmetic average height Ra is large, it has been found that fine irregularities on the surface become shadows during film formation, and many pinholes are formed on the film surface. The average optical density of the portion where the pinhole was formed was less than 4.0.
Therefore, the produced heat-resistant light-shielding film has high blackness and low regular reflectance, but because of the pinholes formed on the film surface, the light-shielding property is insufficient, so it is used for camera modules for mobile phones with cameras. It cannot be used for shutter apertures or shutter blades for digital cameras.

Example 4
A heat-resistant light-shielding multilayer film was produced in the same manner as in Example 1 except that the thickness of the polyimide film was changed to 10 μm, and the types, film thicknesses and compositions of the metal light-shielding film, black coating film and transparent metal compound were the same.
The heat-resistant light-shielding multilayer film has an average optical density of 4 or more at a wavelength of 380 to 780 nm, an average regular reflectance of 0.17%, a film surface brightness (L ^* ) of 32, and zinc oxide (ZnO) -aluminum oxide ( The blackness was increased by forming an (Al ₂ O ₃ ) film. Further, after the production, the sample was left in the atmosphere for 2 weeks, but the color difference (ΔE ^* ab) was calculated to be 0.3, and the color change was invisible to the naked eye.
It was left in the atmosphere for 2 weeks, and it was heated at 100 ° C, 200 ° C, 270 ° C for 30 minutes and treated at a temperature of 85 ° C and a humidity of 85% RH for 500 hours, but there was no change in the average optical density and average regular reflectance. The color difference (ΔE ^* ab) was also 0.1 to 0.4, which was not visible. In the heat resistance test and the adhesion test after the high temperature and high humidity test, the film was not peeled off. Table 1-2 summarizes the characteristics of the heat-resistant and light-shielding multilayer film.
Therefore, the produced heat-resistant light-shielding film has complete light-shielding properties, low specular reflectance, and extremely high blackness, so it can be used as an aperture for camera modules for camera-equipped mobile phones and shutter blades for digital cameras. Is useful.

(Examples 5 to 8)
Except for changing the thickness of the polyimide film to 25 μm (Example 5), 50 μm (Example 6), 100 μm (Example 7), and 250 μm (Example 8), the metal light-shielding film, the black coating film, and the transparent metal compound The heat resistant light-shielding multilayer film was produced in the same manner as in Example 1 in the type, film thickness, and composition.
The average optical density at a wavelength of 380 to 780 nm of the heat-resistant light-shielding multilayer film was 4 or more, and the average regular reflectance was 0.12 to 0.17%, which was the same as in Example 1. Further, the lightness (L ^* ) of the film surface is 26 to 31, and in all cases, the lightness (L ^* ) is reduced by forming a zinc oxide (ZnO) -aluminum oxide (Al ₂ O ₃ ) film, and the blackness is reduced. It became high. Further, after the production, the sample was left in the atmosphere for 2 weeks, but the color difference (ΔE ^* ab) was calculated to be 0.3, and the color change was invisible to the naked eye.
It was left in the atmosphere for 2 weeks, and it was heated at 100 ° C, 200 ° C, 270 ° C for 30 minutes and treated at a temperature of 85 ° C and a humidity of 85% RH for 500 hours, but there was no change in the average optical density and average regular reflectance. The color difference (ΔE ^* ab) was also 0.1 to 0.4, which was not visible. In the heat resistance test and the adhesion test after the high temperature and high humidity test, the film was not peeled off. Table 1-2 summarizes the characteristics of the heat-resistant and light-shielding multilayer film.
Therefore, the heat-resistant light-shielding films produced in Examples 5 to 8 have a complete light-shielding property, a low regular reflectance, and a very high blackness. Therefore, a diaphragm for a camera module for a camera-equipped mobile phone and a shutter for a digital camera Use for blades is useful.

(Comparative Examples 3 and 4)
Except for changing the thickness of the polyimide film to 8 μm (Comparative Example 3) and 260 μm (Comparative Example 4), the types, film thicknesses, and compositions of the metal light-shielding film, black coating film, and transparent metal compound were the same as in Example 1. Thus, a heat-resistant light-shielding film was produced.
The average optical density of the heat-resistant light-shielding film at a wavelength of 380 to 780 nm is 4 or more, and the average regular reflectance is 0.27% (Comparative Example 3) and 0.10% (Comparative Example 4). It was the same. Further, the lightness (L ^* ) of the film surface is 35 (Comparative Example 3) and 28 (Comparative Example 4), both of which are formed by forming a zinc oxide (ZnO) -aluminum oxide (Al ₂ O ₃ ) film. L ^* ) became smaller and the blackness became higher. Further, after the production, the sample was left in the atmosphere for 2 weeks, but the color difference (ΔE ^* ab) was calculated to be 0.3, and the color change was invisible to the naked eye.
It was left in the atmosphere for 2 weeks, and it was heated at 100 ° C, 200 ° C, 270 ° C for 30 minutes and treated at a temperature of 85 ° C and a humidity of 85% RH for 500 hours, but there was no change in the average optical density and average regular reflectance. The color difference (ΔE ^* ab) was also 0.1 to 0.4, which was not visible. In the heat resistance test and the adhesion test after the high temperature and high humidity test, the film was not peeled off.
However, in Comparative Example 3, since the film thickness was thin, many holes were formed in the film during the mat treatment, thereby forming wrinkles in the film, and a sound film could not be produced. On the other hand, since the film thickness is large in Comparative Example 4, it cannot be applied to a camera module whose thickness is reduced. Table 1-2 summarizes the characteristics of the heat-resistant light-shielding film.
Therefore, the heat-resistant light-shielding film produced in Comparative Examples 3 and 4 cannot produce a sound film, and is not suitable for a camera module that is progressing in thickness reduction. Cannot be used for shutter blades for digital cameras.

(Examples 9 and 10)
The composition of the zinc oxide (ZnO) -aluminum oxide (Al ₂ O ₃ ) film is changed to the oxygen content (Al + Zn) by changing the Al ₂ O ₃ content of the zinc oxide (ZnO) -aluminum oxide (Al ₂ O ₃ ) target. The film thicknesses of the metal light-shielding film, the black coating film, and the transparent metal compound are the same as in Example 1 except that the / O atomic ratio is changed to 0.6 (Example 9) and 0.2 (Example 10). Similarly, a heat-resistant and light-shielding multilayer film was produced. Incidentally, zinc oxide (ZnO) - the composition of aluminum oxide _(Al 2 _{O 3)} film, optical glass (manufactured by Corning 7059) of zinc oxide on the (ZnO) - to form an aluminum oxide _(Al 2 _{O 3)} film Samples were prepared and analyzed by XPS.
The heat-resistant light-shielding multilayer film has an average optical density of 4 or more at a wavelength of 380 to 780 nm, an average regular reflectance of 0.10% (Example 9), and 0.20% (Example 10). ^* ) Became 28 (Example 9) and 33 (Example 10), and the blackness increased by forming a zinc oxide (ZnO) -aluminum oxide (Al ₂ O ₃ ) film. Further, after the production, the sample was left in the atmosphere for 2 weeks, but the color difference (ΔE ^* ab) was calculated as 0.6 (Example 9) and 0.4 (Example 10), and the color change was not visually recognized. Met.
It was left in the atmosphere for 2 weeks, and it was heated at 100 ° C, 200 ° C, 270 ° C for 30 minutes and treated at a temperature of 85 ° C and a humidity of 85% RH for 500 hours, but there was no change in the average optical density and average regular reflectance. The color difference (ΔE ^* ab) was also 0.1 to 0.6, which was not visually recognized. In the heat resistance test and the adhesion test after the high temperature and high humidity test, the film was not peeled off. Table 2-1 shows the constitution of the heat-resistant light-shielding multilayer film, and Table 2-2 shows the characteristics.
Accordingly, the heat-resistant light-shielding films produced in Examples 9 and 10 have a complete light-shielding property, a low regular reflectance, and a very high blackness. Therefore, a diaphragm for a camera module for a camera-equipped mobile phone and a shutter blade for a digital camera Use for materials is useful.

(Examples 11-14)
The thickness of the zinc oxide (ZnO) -aluminum oxide (Al ₂ O ₃ ) film was changed to 5 nm (Example 11), 100 nm (Example 12), 200 nm (Example 13), and 250 nm (Example 14). Were the same as in Example 1 in the type, composition, and film thickness of the metal light-shielding film and black coating film, to produce a heat-resistant light-shielding multilayer film.
The average optical density at a wavelength of 380 to 780 nm of the heat-resistant light-shielding multilayer film is 4 or more, and the average regular reflectance is 0.28% (Example 11), 0.16% (Example 12), 0.11% (implementation). Example 13) and 0.08% (Example 14). The lightness (L ^* ) of the film surface was 34 (Example 11), 30 (Example 12), 25 (Example 13), and 20 (Example 14), and zinc oxide (ZnO) -aluminum oxide (Al ₂ O). ₃ ) Blackness became high by forming a film. Further, after the production, the sample was left in the atmosphere for 2 weeks, but the color difference (ΔE ^* ab) was calculated to be 0.3, and the color change was invisible to the naked eye.
It was left in the atmosphere for 2 weeks, and it was heated at 100 ° C, 200 ° C, 270 ° C for 30 minutes and treated at a temperature of 85 ° C and a humidity of 85% RH for 500 hours, but there was no change in the average optical density and average regular reflectance. The color difference (ΔE ^* ab) was also 0.1 to 0.3, which was not visible. In the heat resistance test and the adhesion test after the high temperature and high humidity test, the film was not peeled off. Table 2-2 summarizes the characteristics of the heat-resistant and light-shielding multilayer film.
Therefore, the heat-resistant light-shielding films produced in Examples 11 to 14 have a complete light-shielding property, a low regular reflectance, and a very high blackness. Therefore, an aperture for a camera module for a camera-equipped mobile phone or a shutter for a digital camera is used. Use for blades is useful.

(Comparative Example 5)
Except for not forming a zinc oxide (ZnO) -aluminum oxide (Al ₂ O ₃ ) film as an antioxidant film, the types, compositions, and film thicknesses of the metal light-shielding film and the black coating film are the same as those in Example 1. Similarly, a heat-resistant light-shielding film was produced.
The average optical density of the heat-resistant light-shielding film at a wavelength of 380 to 780 nm was 4 or more, and the average regular reflectance was 0.30%. The brightness (L ^* ) of the film surface was 35. Further, after the production, the sample was left in the atmosphere for 2 weeks, but the color difference (ΔE ^* ab) was calculated to be 2.3, and the color change was of a level that can be visually recognized.
The sample was left in the atmosphere for 2 weeks, heated at 100 ° C., 200 ° C., 270 ° C. for 30 minutes or treated at a temperature of 85 ° C. and a humidity of 85% RH for 500 hours, but there was almost no change in average optical density and average regular reflectance. However, under heating at 200 ° C. or higher and high temperature and high humidity, the color difference (ΔE ^* ab) changed from 1.3 to 2.3 until it was sufficiently visually confirmed. In the heat resistance test and the adhesion test after the high temperature and high humidity test, the film was not peeled off. Table 2-2 summarizes the characteristics of the heat-resistant light-shielding film.
Therefore, the heat-resistant light-shielding film produced in Comparative Example 5 changes in film color when left in the atmosphere and in a high temperature and high temperature and high humidity environment, but has high light shielding properties and low regular reflection, and has high blackness. Therefore, it can be used for a diaphragm for a camera module for a mobile phone with a camera and a shutter blade for a digital camera.

(Comparative Examples 6 and 7)
Except for changing the thickness of the zinc oxide (ZnO) -aluminum oxide (Al ₂ O ₃ ) film to 4 nm (Comparative Example 6) and 260 nm (Comparative Example 7), the types and compositions of the metal light-shielding film and the black coating film The film thickness was the same as in Example 1 to produce a heat-resistant light-shielding film.
The average optical density at a wavelength of 380 to 780 nm of the heat-resistant light-shielding film was 4 or more, and the average regular reflectance was 0.32% (Comparative Example 6) and 0.08% (Comparative Example 7). The lightness (L ^* ) on the film surface was 36 (Comparative Example 6) and 20 (Comparative Example 7). Further, after the production, the sample was left in the atmosphere for 2 weeks, but the color difference (ΔE ^* ab) was calculated to be 1.8 in Comparative Example 6 and 0.5 in Comparative Example 7, and the color change was visually observed in Comparative Example 6. It was understandable.
The sample was left in the atmosphere for 2 weeks, heated at 100 ° C., 200 ° C., 270 ° C. for 30 minutes, or treated at a temperature of 85 ° C. and a humidity of 85% RH for 500 hours. However, the color difference (ΔE ^* ab) was 0.1 to 0.5 and was not visually confirmed. In the heat resistance test and the adhesion test after the high temperature and high humidity test, the film was not peeled off. Table 2-2 summarizes the characteristics of the heat-resistant light-shielding film.
Therefore, since the heat-resistant light-shielding film produced in Comparative Example 6 has a thin transparent metal compound film, the film color changes when left in the atmosphere for 2 weeks, but has high light-shielding properties and low regular reflection properties. Since the degree of blackness is high, it can be sufficiently used for an aperture for a camera module for a camera-equipped mobile phone or a shutter blade for a digital camera.
In addition, the heat-resistant light-shielding film produced in Comparative Example 7 has a thick transparent metal compound film, so when considering productivity such as manufacturing cost, the aperture for a camera module for a camera-equipped mobile phone is required to be reduced in cost. It cannot be used for shutter blades for digital cameras.

(Examples 15 to 18)
The target for forming the transparent metal compound film is aluminum (Al), oxygen gas is introduced, and the material of the transparent metal compound film is changed to aluminum oxide (Al ₂ O ₃ ) by reactive sputtering, and the film thickness of the transparent metal compound film The types, compositions, and thicknesses of the metal light-shielding film and the black coating film are the same except that the thickness is 5 nm (Example 15), 100 nm (Example 16), 200 nm (Example 17), and 250 nm (Example 18). In the same manner as in Example 1, a heat resistant light-shielding multilayer film was produced. The oxygen content in aluminum oxide (Al ₂ O ₃ ) was 0.4 as the Al / O atomic ratio.
The average optical density at a wavelength of 380 to 780 nm of the heat-resistant light-shielding multilayer film is 4 or more, and the average regular reflectance is 0.29% (Example 15), 0.15% (Example 16), 0.09% (implementation). Example 17) and 0.07% (Example 18). The film surface lightness (L ^* ) is 34 (Example 15), 24 (Example 16), 23 (Example 17), and 21 (Example 18), and an aluminum oxide (Al ₂ O ₃ ) film is formed. As a result, the blackness increased. In addition, after the preparation, the sample was left in the atmosphere for 2 weeks, but the color difference (ΔE ^* ab) was calculated to be 0.5, and the color change was invisible to the naked eye.
It was left in the atmosphere for 2 weeks, and it was heated at 100 ° C, 200 ° C, 270 ° C for 30 minutes and treated at a temperature of 85 ° C and a humidity of 85% RH for 500 hours, but there was no change in the average optical density and average regular reflectance. The color difference (ΔE ^* ab) was 0.1 to 0.5, which was not visually recognized. In the heat resistance test and the adhesion test after the high temperature and high humidity test, the film was not peeled off. Table 2-2 summarizes the characteristics of the heat-resistant and light-shielding multilayer film.
Accordingly, the heat-resistant light-shielding films produced in Examples 15 to 18 have a complete light-shielding property, low regular reflectance, and very high blackness. Therefore, an aperture for a camera module for a camera-equipped mobile phone and a shutter for a digital camera are used. Use for blades is useful.

(Comparative Examples 8 and 9)
Except for changing the film thickness of the aluminum oxide (Al ₂ O ₃ ) film to 4 nm (Comparative Example 8) and 260 nm (Comparative Example 9), the types, compositions, and film thicknesses of the metal light-shielding film and the black coating film are examples. In the same manner as in Example 15, a heat-resistant light-shielding film was produced.
The average optical density at a wavelength of 380 to 780 nm of the heat-resistant light-shielding film was 4 or more, and the average regular reflectance was 0.30% (Comparative Example 8) and 0.07% (Comparative Example 9). The brightness (L ^* ) of the film surface was 35 (Comparative Example 8) and 20 (Comparative Example 9). Further, after the production, the sample was left in the atmosphere for 2 weeks, but the color difference (ΔE ^* ab) was calculated as 1.5 (Comparative Example 8) and 0.6 (Comparative Example 9). It was a level that can be visually confirmed.
Although it was left in the atmosphere for 2 weeks and heated at 100 ° C., 200 ° C., 270 ° C. for 30 minutes and treated at a temperature of 85 ° C. and a humidity of 85% RH for 500 hours, there was almost no change in average optical density and average regular reflectance. The color difference (ΔE ^* ab) was 0.1 to 0.6, which was not visible. In the heat resistance test and the adhesion test after the high temperature and high humidity test, the film was not peeled off. Table 2-2 summarizes the characteristics of the heat-resistant light-shielding film.
Therefore, the heat-resistant light-shielding film produced in Comparative Example 8 changes its film color when left in the atmosphere for 2 weeks, but it has a high light-shielding property, low regular reflection property, and high blackness, so that it is sufficiently It can be used as an aperture for camera modules for mobile phones with a mobile phone and shutter blades for digital cameras.
In addition, the heat-resistant light-shielding film produced in Comparative Example 9 has a thick transparent metal compound film, so when considering productivity such as manufacturing cost, the aperture for a camera module for a camera-equipped mobile phone is required to be reduced in cost. It cannot be used for shutter blades for digital cameras.

(Examples 19 and 20)
Except for changing the oxygen gas amount and changing the oxygen content of the aluminum oxide film (Al ₂ O ₃ film) to 0.6 (Example 19) and 0.1 (Example 20) as the Al / O atomic ratio. A heat-resistant light-shielding multilayer film was produced in the same manner as in Example 15 except for the type, composition, and film thickness of the metal light-shielding film and black coating film.
The average optical density at a wavelength of 380 to 780 nm of the heat-resistant light-shielding multilayer film was 4 or more, and the average regular reflectance was 0.29% (Example 19) and 0.20 (Example 20). The lightness (L ^* ) of the film surface was 34 (Example 19) and 25 (Example 20), and the blackness was increased by forming an aluminum oxide (Al ₂ O ₃ ) film. Further, after the production, the sample was left in the atmosphere for 2 weeks, but the color difference (ΔE ^* ab) was calculated to be 0.7, and the color change was invisible to the naked eye.
It was left in the atmosphere for 2 weeks, and it was heated at 100 ° C, 200 ° C, 270 ° C for 30 minutes and treated at a temperature of 85 ° C and a humidity of 85% RH for 500 hours. The color difference (ΔE ^* ab) was also 0.1 to 0.7, which was not visible. In the heat resistance test and the adhesion test after the high temperature and high humidity test, the film was not peeled off. Table 2-2 summarizes the characteristics of the heat-resistant and light-shielding multilayer film.
Therefore, the heat-resistant light-shielding films produced in Examples 19 to 20 have a complete light-shielding property, a low regular reflectance, and a very high blackness. Therefore, a diaphragm for a camera module for a camera-equipped mobile phone and a shutter for a digital camera Use for blades is useful.

(Examples 21 to 24)
The target for forming the transparent metal compound film is an Si target, the material of the transparent metal compound film formed by reactive sputtering by introducing oxygen gas is changed to silicon dioxide (SiO ₂ ), and the film thickness is 5 nm (Example 21), 100 nm. Except for changing to (Example 22), 200 nm (Example 23), and 250 nm (Example 24), the types, compositions, and film thicknesses of the metal light-shielding film and the black coating film were the same as in Example 1, and the heat resistance was changed. A light-shielding multilayer film was produced. The composition of the silicon dioxide film was 0.5 as the Si / O atomic ratio.
The average optical density at a wavelength of 380 to 780 nm of the heat-resistant light-shielding multilayer film is 4 or more, and the average regular reflectance is 0.29% (Example 21), 0.23% (Example 22), 0.18% (implemented) Example 23) and 0.12% (Example 24). The lightness (L ^* ) of the film surface is 34 (Example 21), 34 (Example 22), 30 (Example 23), and 26 (Example 24), and a silicon dioxide (SiO ₂ ) film is formed. Blackness became high. Further, after the production, the sample was left in the atmosphere for 2 weeks, but the color difference (ΔE ^* ab) was calculated to be 0.7, and the color change was invisible to the naked eye.
It was left in the atmosphere for 2 weeks, and it was heated at 100 ° C, 200 ° C, 270 ° C for 30 minutes and treated at a temperature of 85 ° C and a humidity of 85% RH for 500 hours. The color difference (ΔE ^* ab) was also 0.1 to 0.7, which was not visible. In the heat resistance test and the adhesion test after the high temperature and high humidity test, the film was not peeled off. Table 2-2 summarizes the characteristics of the heat-resistant and light-shielding multilayer film.
Therefore, the heat-resistant light-shielding films produced in Examples 21 to 24 have a complete light-shielding property, a low regular reflectance, and a very high blackness. Therefore, an aperture for a camera module for a camera-equipped mobile phone or a shutter for a digital camera is used. Use for blades is useful.

(Comparative Examples 10 and 11)
Except for changing the film thickness of silicon dioxide (SiO ₂ ) of the transparent metal compound film to 4 nm (Comparative Example 10) and 260 nm (Comparative Example 11), the types, compositions, and film thicknesses of the metal light-shielding film and the black coating film are as follows. In the same manner as in Example 21, a heat-resistant light-shielding film was produced.
The average optical density at a wavelength of 380 to 780 nm of the heat-resistant light-shielding film was 4 or more, and the average regular reflectance was 0.30% (Comparative Example 10) and 0.12% (Comparative Example 11). The lightness (L ^* ) of the film surface was 35 (Comparative Example 10) and 26 (Comparative Example 11). Further, after the production, it was left in the atmosphere for 2 weeks, but the color difference (ΔE ^* ab) was calculated as 1.4 (Comparative Example 10) and 0.7 (Comparative Example 11). It was a level that can be visually confirmed.
Standing in the atmosphere for 2 weeks, heating at 100 ° C., 200 ° C., 270 ° C. for 30 minutes or treating at a temperature of 85 ° C. and a humidity of 85% RH for 500 hours. The average specular reflectance changed under high temperature and high humidity, and the color difference exceeded 1.0. However, in Comparative Example 11, the color difference (ΔE ^* ab) was 0.1 to 0.8, which was invisible. It was. In the heat resistance test and the adhesion test after the high temperature and high humidity test, the film was not peeled off. Table 2-2 summarizes the characteristics of the heat-resistant light-shielding film.
Therefore, since the heat-resistant light-shielding film produced in Comparative Example 10 has a thin transparent metal oxide film, the film color changes when left in the atmosphere for 2 weeks or at a high temperature of 200 ° C. or higher and a high temperature and high humidity environment. However, since it has high light-shielding properties and low regular reflection properties and high blackness, it can be sufficiently used for an aperture for a camera module for a camera-equipped mobile phone or a shutter blade material for a digital camera.
Further, the heat-resistant light-shielding film produced in Comparative Example 11 has a thick transparent metal compound film, so that when considering productivity such as manufacturing cost, the aperture for a camera module for a camera-equipped mobile phone is required to be reduced in cost. It cannot be used for shutter blades for digital cameras.

(Examples 25 and 26)
Except for changing the amount of oxygen introduced during the formation of the silicon dioxide film and changing the Si / O atomic ratio in the film to 0.7 (Example 25) and 0.2 (Example 26), the metal light-shielding film, black coating A heat-resistant light-shielding multilayer film was produced in the same manner as in Example 1 with respect to the type, composition, and film thickness of the coating film.
The average optical density at a wavelength of 380 to 780 nm of the heat-resistant light-shielding multilayer film was 4 or more, and the average regular reflectance was 0.15% (Example 25) and 0.10% (Example 26). The lightness (L ^* ) of the film surface was 29 (Example 25) and 27 (Example 26), and the blackness was increased by forming a silicon dioxide (SiO ₂ ) film. Further, after the production, the sample was left in the atmosphere for 2 weeks, but the color difference (ΔE ^* ab) was calculated to be 0.7, and the color change was invisible to the naked eye.
It was left in the atmosphere for 2 weeks, and it was heated at 100 ° C, 200 ° C, 270 ° C for 30 minutes and treated at a temperature of 85 ° C and a humidity of 85% RH for 500 hours. The color difference (ΔE ^* ab) was also 0.1 to 0.7, which was not visible. In the heat resistance test and the adhesion test after the high temperature and high humidity test, the film was not peeled off. Table 2-2 summarizes the characteristics of the heat-resistant and light-shielding multilayer film.
Therefore, the heat-resistant light-shielding films produced in Examples 25 and 26 have a complete light-shielding property, a low regular reflectance, and a very high blackness. Therefore, an aperture for a camera module for a camera-equipped mobile phone or a shutter for a digital camera is used. Use for blades is useful.

(Example 27)
A metal light-shielding film, except that the transparent metal compound film forming target is a titanium (Ti) target and the type of the transparent metal oxide film is changed to a titanium oxide film (TiO ₂ ) formed by introducing oxygen gas, The kind, composition, and thickness of the black coating film were the same as in Example 1, and a heat-resistant and light-shielding multilayer film was produced. The composition of the titanium oxide film was 0.4 as the Ti / O atomic ratio.
The average optical density of the heat resistant light-shielding multilayer film at a wavelength of 380 to 780 nm was 4 or more, and the average regular reflectance was 0.20%. The lightness (L ^* ) of the film surface was 30, and the blackness was increased by forming the titanium oxide film. Further, after the production, the sample was left in the atmosphere for 2 weeks, but the color difference (ΔE ^* ab) was calculated to be 0.8, and the color change was invisible to the naked eye.
It was left in the atmosphere for 2 weeks, and it was heated at 100 ° C, 200 ° C, 270 ° C for 30 minutes and treated at a temperature of 85 ° C and a humidity of 85% RH for 500 hours, but there was no change in the average optical density and average regular reflectance. The color difference (ΔE ^* ab) was also 0.1 to 0.8, which was not visually recognized. In the heat resistance test and the adhesion test after the high temperature and high humidity test, the film was not peeled off. Table 2-2 summarizes the characteristics of the heat-resistant and light-shielding multilayer film.
Therefore, the heat-resistant light-shielding film produced in Example 27 has a complete light-shielding property, low regular reflectance, and very high blackness. Therefore, an aperture for a camera module for a camera-equipped mobile phone and a shutter blade material for a digital camera are used. It is useful for use.

(Examples 28 to 31)
Types of metal light-shielding film and black coating film except that the thickness of the titanium oxide film was changed to 5 nm (Example 28), 100 nm (Example 29), 200 nm (Example 30), and 250 nm (Example 31). The composition and film thickness were the same as in Example 27, and a heat-resistant and light-shielding multilayer film was produced.
The optical density, regular reflectance, brightness, and color difference of the produced heat-resistant and light-shielding multilayer film were the same as in Example 27 as shown in Table 2-2.
The sample was allowed to stand in the atmosphere for 2 weeks, heated at 100 ° C., 200 ° C., 270 ° C. for 30 minutes and treated at a temperature of 85 ° C. and a humidity of 85% RH for 500 hours. And the color difference (ΔE ^* ab) was 0.1 to 0.8, which was invisible to the naked eye. In the heat resistance test and the adhesion test after the high temperature and high humidity test, the film was not peeled off.
Therefore, the heat-resistant light-shielding multilayer film produced in Examples 28 to 31 has a complete light-shielding property, low regular reflectance, and very high blackness. Use for shutter blades is useful.

(Comparative Examples 12 and 13)
Except for changing the thickness of the transparent metal compound film of titanium oxide (TiO ₂ ) to 4 nm (Comparative Example 12) and 260 nm (Comparative Example 13), the types, compositions, and thicknesses of the metal light-shielding film and the black coating film are as follows. A heat resistant light-shielding film was produced in the same manner as in Example 27.
The average optical density at a wavelength of 380 to 780 nm of the heat-resistant light-shielding film was 4 or more, and the average regular reflectance was 0.25% (Comparative Example 12) and 0.08% (Comparative Example 13). The brightness (L ^* ) on the film surface was 34 (Comparative Example 12) and 24 (Comparative Example 13). In addition, although the color difference (ΔE ^* ab) was calculated as 2.0 (Comparative Example 12) and 0.8 (Comparative Example 13) after two weeks in the air after production, the color change was visually observed in Comparative Example 10. It was just enough to understand.
The sample was allowed to stand in the atmosphere for 2 weeks and heated at 100 ° C., 200 ° C., and 270 ° C. for 30 minutes and treated at a temperature of 85 ° C. and a humidity of 85% RH for 500 hours, but in Comparative Example 12, it was left in the air and heated at 270 ° C. The average regular reflectance changed under high temperature and high humidity, and the color difference (ΔE ^* ab) changed to 1.4 to 2.0 to the extent that can be visually confirmed. On the other hand, also in Comparative Example 13, the color difference was 0.1 to 0.8 and was not visually confirmed. In the heat resistance test and the adhesion test after the high temperature and high humidity test, the film was not peeled off. Table 2 summarizes the characteristics of the heat-resistant light-shielding film.
On the other hand, in Comparative Example 13, the film did not peel off in the heat resistance test or the adhesion test after the high temperature and high humidity test. Table 2-2 summarizes the characteristics of the heat-resistant light-shielding film.
Therefore, the heat-resistant light-shielding film produced in Comparative Example 12 has a thin transparent metal oxide film, so that the film color changes when left in the atmosphere for 2 weeks. Since the degree of blackness is high, it can be sufficiently used for an aperture for a camera module for a camera-equipped mobile phone or a shutter blade for a digital camera.
In addition, the heat-resistant light-shielding film produced in Comparative Example 13 has a thick transparent metal compound film, so when considering productivity such as manufacturing cost, the aperture for a camera module for a camera-equipped mobile phone is required to be reduced in cost. It cannot be used for shutter blades for digital cameras.

(Examples 32 and 33)
Except for changing the amount of oxygen introduced during the formation of the titanium oxide film and changing the Ti / O atomic ratio in the film to 0.6 (Example 32) and 0.2 (Example 33), the metal light-shielding film, black coating A heat-resistant light-shielding multilayer film was produced in the same manner as in Example 1 with respect to the type, composition, and film thickness of the coating film.
The produced heat resistant light-shielding multilayer film had the same average optical density, average regular reflectance, color, and color difference as those of Example 27.
It was left in the atmosphere for 2 weeks, and it was heated at 100 ° C, 200 ° C, 270 ° C for 30 minutes and treated at a temperature of 85 ° C and a humidity of 85% RH for 500 hours, but there was no change in the average optical density and average regular reflectance. The color difference (ΔE ^* ab) was also 0.1 to 0.8, which was not visually recognized. In the heat resistance test and the adhesion test after the high temperature and high humidity test, the film was not peeled off. Table 2-2 summarizes the characteristics of the heat-resistant and light-shielding multilayer film.
Therefore, since the heat-resistant light-shielding multilayer film produced in Examples 32 and 33 has a complete light-shielding property, a low regular reflectance, and a very high blackness, it is suitable for a diaphragm for a camera module for a camera-equipped mobile phone or a digital camera. Use for shutter blades is useful.

(Examples 34 to 37)
Except for changing the film thickness of the metal light-shielding film to 40 nm (Example 34), 100 nm (Example 35), 200 nm (Example 36), and 250 nm (Example 37), A heat-resistant light-shielding multilayer film was produced in the same manner as in Example 1 in terms of type, composition, and film thickness.
The optical density, regular reflectance, brightness, and color difference of the produced heat-resistant and light-shielding multilayer film were the same as in Example 1 as shown in Table 2-2.
The sample was allowed to stand in the atmosphere for 2 weeks and heated at 100 ° C., 200 ° C., 270 ° C. for 30 minutes and treated at a temperature of 85 ° C. and a humidity of 85% RH for 500 hours. No change was observed, and the color difference (ΔE ^* ab) was 0.1 to 0.3. In the heat resistance test and the adhesion test after the high temperature and high humidity test, the film was not peeled off.
Therefore, the heat-resistant light-shielding multilayer film produced in Examples 34 to 37 has a complete light-shielding property, a low regular reflectance, and a very high blackness. Therefore, the diaphragm for a camera module for a mobile phone with a camera and a digital camera Use for shutter blades is useful.

(Comparative Examples 14 and 15)
Except for changing the thickness of the metal light-shielding film to 30 nm (Comparative Example 14) and 260 nm (Comparative Example 15), the types, compositions, and thicknesses of the black coating film and the transparent metal compound film were the same as in Example 1. A heat-resistant light-shielding film was produced.
The average regular reflectance, brightness, and color difference of the heat-resistant light-shielding film produced in Comparative Example 14 were the same as in Example 1 as shown in Table 2-2, but the average optical density was 3.4 and the optical density was 4 Was less than. In Comparative Example 15, the optical density was 4 or more, but the average regular reflectance and L * were higher than those in Example 1.
The sample was allowed to stand in the atmosphere for 2 weeks and heated at 100 ° C., 200 ° C., 270 ° C. for 30 minutes and treated at a temperature of 85 ° C. and a humidity of 85% RH for 500 hours. No change was observed, and the color difference (ΔE ^* ab) was 0.1 to 0.3. In the heat resistance test and the adhesion test after the high temperature and high humidity test, the film was not peeled off.
Therefore, the heat-resistant light-shielding film produced in Comparative Example 14 has a low regular reflectance and a very high blackness, but has an average optical density of 3.4 and no light-shielding property. Cannot be used for shutter apertures and shutter blades for digital cameras. On the other hand, in Comparative Example 15, since the metal light-shielding film is very thick, the average regular reflectance is high, and the camera module for a camera-equipped mobile phone is required to reduce costs when productivity such as manufacturing cost is considered. It cannot be used as a diaphragm for shutters or shutter blades for digital cameras.

(Examples 38 to 40)
A black coating film and a transparent metal compound film except that the type of the metal light-shielding film is a titanium carbide oxide film and the film thickness is changed to 40 nm (Example 38), 120 nm (Example 39), and 250 nm (Example 40). The heat resistant light-shielding multilayer film was produced in the same manner as in Example 1 in the type, composition, and film thickness. The composition of the carbonized titanium oxide film (C / Ti atomic ratio, O / Ti atomic ratio) is shown in Table 2-1.
The optical density, regular reflectance, brightness, and color difference of the produced heat-resistant and light-shielding multilayer film were the same as in Example 1 as shown in Table 2-2.
The sample was allowed to stand in the atmosphere for 2 weeks, heated at 100 ° C., 200 ° C., 270 ° C. for 30 minutes and treated at a temperature of 85 ° C. and a humidity of 85% RH for 500 hours. No change was observed, and the color difference (ΔE ^* ab) was 0.1 to 0.6. In the heat resistance test and the adhesion test after the high temperature and high humidity test, the film was not peeled off.
Therefore, the heat-resistant light-shielding multilayer films produced in Examples 38 to 40 have a complete light-shielding property, a low regular reflectance, and a very high blackness. Therefore, the diaphragm for a camera module for a camera-equipped mobile phone or a digital camera Use for shutter blades is useful.

(Comparative Example 16)
Except for changing the thickness of the titanium carbide oxide film of the metal light-shielding film to 28 nm, the composition of the metal light-shielding film, the types, compositions, and film thicknesses of the black coating film and the transparent metal compound film are the same as in Example 38. A light shielding film was prepared. The composition of the carbonized titanium oxide film (C / Ti atomic ratio, O / Ti atomic ratio) is shown in Table 2-1.
The average regular reflectance, brightness, and color difference of the heat-resistant light-shielding film produced were the same as in Example 1 as shown in Table 2-2. However, the average optical density was 3.2 and less than 4, and the light shielding property was insufficient. I found out.
The sample was allowed to stand in the atmosphere for 2 weeks, heated at 100 ° C., 200 ° C., 270 ° C. for 30 minutes and treated at a temperature of 85 ° C. and a humidity of 85% RH for 500 hours. No change was observed, and the color difference (ΔE ^* ab) was 0.1 to 0.6, which was invisible to the naked eye. In the heat resistance test and the adhesion test after the high temperature and high humidity test, the film was not peeled off.
Therefore, the heat-resistant light-shielding film produced in Comparative Example 16 has a low regular reflectance and a very high blackness, but lacks light-shielding properties. Therefore, a diaphragm for a camera module for a camera-equipped mobile phone or a digital camera Cannot be used for shutter blades for

(Examples 41 to 43)
A black coating film, transparent, except that the type of the metal light-shielding film is a nickel titanium (NiTi) film and the film thickness is changed to 40 nm (Example 41), 120 nm (Example 42), and 250 nm (Example 43). A heat-resistant light-shielding multilayer film was produced in the same manner as in Example 1 in terms of the type, composition, and film thickness of the metal compound film.
The average optical density, average regular reflectance, brightness, and color difference of the produced heat-resistant light-shielding multilayer film were the same as in Example 1 as shown in Table 2-2.
Standing in the atmosphere for 2 weeks, heating at 100 ° C., 200 ° C., 270 ° C. for 30 minutes and treating at a temperature of 85 ° C. and a humidity of 85% RH for 500 hours. In the treatment at 85% RH, the average optical density and the average regular reflectance were not changed as in Example 1, and the color difference (ΔE ^* ab) was 0.6, which was not visually recognized. However, when heated at 270 ° C., the film color changed due to the change in the optical constant indicating the film characteristics due to the oxidation of the NiTi film. In the heat resistance test and the adhesion test after the high temperature and high humidity test, the film was not peeled off.
Therefore, the heat-resistant light-shielding multilayer film produced in Examples 41 to 43 has a perfect light-shielding property, a low regular reflectance, and a very high blackness, but for a mobile phone with a camera used in a use environment of 200 ° C. or less. Use for a diaphragm for a camera module or a shutter blade for a digital camera is useful.

(Comparative Examples 17 and 18)
Except for changing the thickness of the NiTi film of the metal light-shielding film to 30 nm (Comparative Example 17) and 260 nm (Comparative Example 18), the types, compositions, and thicknesses of the black coating film and the transparent metal compound film are the same as in Example 41. Similarly, a heat-resistant light-shielding film was produced.
The average regular reflectance, brightness, and color difference of the heat-resistant light-shielding films prepared in Comparative Examples 17 and 18 were the same as in Example 41 as shown in Table 2, but in Comparative Example 17, the average optical density was 3.4. It became less than 4 and it turned out that the light-shielding property is insufficient. On the other hand, in Comparative Example 18, the average regular reflectance and lightness (L *) were higher than in Example 41.
When heated at 100 ° C., 200 ° C. and 270 ° C. for 30 minutes in the atmosphere, the film color changes, the average regular reflectance changes, and the color difference (ΔE ^* ab) also changes. It deteriorated to 1.5 by heating at 270 ° C. for 30 minutes. However, in these heat resistance tests and adhesion tests after the high temperature and high humidity test, the film was not peeled off.
Therefore, the heat-resistant light-shielding film produced in Comparative Example 17 has a low regular reflectance and a very high blackness, but lacks light-shielding properties. Therefore, a diaphragm or a digital camera for a camera module for a mobile phone with a camera is used. Cannot be used for shutter blades for In Comparative Example 18, since the metal light-shielding film is thick, when considering productivity such as manufacturing cost, an aperture for a camera module for a camera-equipped mobile phone and a shutter blade for a digital camera are required to be reduced in cost. It cannot be used for materials.

(Examples 44 and 45)
Except for changing the type of the metal light-shielding film to titanium (Ti: Example 44) and aluminum (Al: Example 45), the types, compositions, and film thicknesses of the black coating film and the transparent metal compound film are the same as in Example 1. Similarly, a heat-resistant and light-shielding multilayer film was produced.
The average optical density, average regular reflectance, brightness, and color difference of the produced heat-resistant light-shielding multilayer film were the same as in Example 1 as shown in Table 2-2.
The sample was allowed to stand in the atmosphere for 2 weeks and heated at 100 ° C., 200 ° C., 270 ° C. for 30 minutes and treated at a temperature of 85 ° C. and a humidity of 85% RH for 500 hours. No change was observed, and the color difference (ΔE ^* ab) was 0.1 to 0.7. In the heat resistance test and the adhesion test after the high temperature and high humidity test, the film was not peeled off.
Therefore, the heat-resistant light-shielding multilayer film produced in Examples 44 and 45 has a complete light-shielding property, a low regular reflectance, and a very high blackness. Therefore, the diaphragm for a camera module for a mobile phone with a camera or a digital camera Use for shutter blades is useful.

(Examples 46 to 48)
The type of black coating film is titanium carbide oxide, and the composition is 0.7 (Example 46), 1.0 (Example 47), 1.4 (Example 48) as the O / Ti atomic ratio in the film. A heat-resistant light-shielding multilayer film was produced in the same manner as in Example 1 except that the metal light-shielding film and the transparent metal compound film were changed.
As shown in Table 3, the average optical density, average regular reflectance, brightness, and color difference of the produced heat-resistant light-shielding multilayer film were the same as in Example 1.
The sample was allowed to stand in the atmosphere for 2 weeks and heated at 100 ° C., 200 ° C., 270 ° C. for 30 minutes and treated at a temperature of 85 ° C. and a humidity of 85% RH for 500 hours. The color difference (ΔE ^* ab) was less than 1.0, which was invisible to the naked eye. In the heat resistance test and the adhesion test after the high temperature and high humidity test, the film was not peeled off. Table 3-1 shows the constitution of the heat-resistant light-shielding multilayer film, and Table 3-2 shows the characteristics.
Therefore, the heat-resistant light-shielding multilayer films produced in Examples 46 to 48 have a complete light-shielding property, a low regular reflectance, and a very high blackness. Use for shutter blades is useful.

(Comparative Examples 19 and 20)
The metal light-shielding film except that the composition of the titanium carbide oxide film as the black coating film was changed to 0.6 (Comparative Example 19) and 1.5 (Comparative Example 20) as the O / Ti atomic ratio in the film. The type, composition, and thickness of the transparent metal compound film were the same as in Example 1 to produce a heat-resistant light-shielding film.
The average optical density of the heat-resistant light-shielding film produced in Comparative Example 19 was 4 or more, but the average regular reflectance was 0.35% and the brightness was 39. The average regular reflectance was higher than that in Example 1, and the brightness was I found it expensive. The color difference was the same as in Example 1 as shown in Table 3. On the other hand, in Comparative Example 20, after the production, the color difference after standing for 2 weeks in the atmosphere was 1.2, and the color change was found visually.
The sample was allowed to stand in the atmosphere for 2 weeks and heated at 100 ° C., 200 ° C., 270 ° C. for 30 minutes and treated at a temperature of 85 ° C. and a humidity of 85% RH for 500 hours. There was no change in the average regular reflectance, and the color difference (ΔE ^* ab) was less than 1.0, which was invisible to the naked eye. However, in Comparative Example 20, the average regular reflectance changed under heating at 270 ° C. and under high temperature and high humidity, and the color difference (ΔE ^* ab) was also about 1.2 to 1.3.
In the heat resistance test and the adhesion test after the high temperature and high humidity test, the film was not peeled off.
Therefore, although the heat-resistant light-shielding film produced in Comparative Example 19 has high regular reflectance and lightness, but has good light-shielding properties, it can be used as an aperture for camera modules for camera-equipped mobile phones and shutter blades for digital cameras Can be used. Further, in Comparative Example 20, although the color difference after fabrication is large, it has a light shielding property and has a low average regular reflectance. Can do.

(Examples 49 to 51)
Except for changing the thickness of the black coating film to 50 nm (Example 49), 200 nm (Example 50), and 250 nm (Example 51), the types, compositions, and thicknesses of the metal light-shielding film and the transparent metal compound film are as follows. A heat-resistant and light-shielding multilayer film was produced in the same manner as in Example 1.
As shown in Table 3, the average optical density, average regular reflectance, brightness, and color difference of the produced heat-resistant light-shielding multilayer film were the same as in Example 1.
The sample was allowed to stand in the atmosphere for 2 weeks and heated at 100 ° C., 200 ° C., 270 ° C. for 30 minutes and treated at a temperature of 85 ° C. and a humidity of 85% RH for 500 hours. No change was observed, and the color difference (ΔE ^* ab) was 0.1 to 0.7. In the heat resistance test and the adhesion test after the high temperature and high humidity test, the film was not peeled off.
Therefore, the heat-resistant light-shielding multilayer film produced in Examples 49 to 51 has a complete light-shielding property, a low regular reflectance, and a very high blackness. Therefore, the diaphragm for a camera module for a camera-equipped mobile phone or a digital camera Use for shutter blades is useful.

(Comparative Examples 21 and 22)
Except for changing the film thickness of the titanium carbide oxide film, which is a black coating film, to 40 nm (Comparative Example 21) and 260 nm (Comparative Example 22), the types, compositions, and film thicknesses of the metal light-shielding film and the transparent metal compound film were implemented. A heat-resistant light-shielding film was produced in the same manner as in Example 49.
The color difference after leaving the heat-resistant light-shielding film produced in Comparative Example 21 in the atmosphere for 2 weeks was equivalent to that in Example 49, but the average regular reflectance and brightness were as shown in Table 49. It was found to be expensive. Further, Comparative Example 22 had the same characteristics as Example 1.
The sample was allowed to stand in the atmosphere for 2 weeks, heated at 100 ° C., 200 ° C., 270 ° C. for 30 minutes and treated at a temperature of 85 ° C. and a humidity of 85% RH for 500 hours. No change was observed, and the color difference (ΔE ^* ab) was 0.1 to 0.7. In the heat resistance test and the adhesion test after the high temperature and high humidity test, the film was not peeled off.
Therefore, the heat-resistant light-shielding film produced in Comparative Example 21 has a high average regular reflectance and lightness, but has good light-shielding properties. Therefore, it can be used as an aperture for camera modules for camera-equipped mobile phones and a shutter blade material for digital cameras. Can be used. Further, in Comparative Example 22, since the thickness of the black coating film is large, when considering productivity such as manufacturing cost, an aperture for a camera module for a camera-equipped mobile phone and a shutter blade for a digital camera are required to be reduced in cost. It cannot be used for materials.

(Example 52)
Except for changing the material of the black coating film to titanium oxide, the type, film thickness and composition of the metal light-shielding film and the transparent metal compound, the film thickness of the black coating film, the material and thickness of the resin film, and the arithmetic average height Ra Produced a heat-resistant light-shielding multilayer film in the same manner as in Example 1.
The target for forming a titanium oxide film was prepared from a mixture of titanium oxide and titanium metal powder by a hot press sintering method. The O / Ti atomic ratio of the sintered compact target was controlled according to the blending ratio of titanium oxide and metal titanium.
On the titanium carbide film formed on the surface of the polyimide film subjected to the sandblast treatment, the film forming gas pressure was adjusted to 6.0 Pa using a titanium oxide target to form a titanium oxide film having a thickness of 105 nm. The brightness (L ^* ) of the titanium carbide film and the titanium oxide film laminated film formed on the polyimide film was measured and found to be 35.
Further, a sample in which a titanium oxide film was similarly formed on optical glass (Corning Corp .: 7059) was also produced. As a result of analyzing the composition of the titanium oxide film formed on the optical glass by XPS (X-ray photoelectron emission analyzer), the oxygen content in the film was 0.84 as the O / Ti atomic ratio.
Further, a zinc oxide (ZnO) -aluminum oxide (ZnO) -aluminum oxide (Al ₂ O ₃ ) target is used on a laminated film of a titanium carbide film and a titanium oxide film sequentially formed on a polyimide film. An Al ₂ O ₃ ) film having a thickness of 15 nm was formed to produce a heat-resistant light-shielding film.
The average optical density at a wavelength of 380 to 780 nm of a heat-resistant light-shielding film comprising a titanium carbide film, a titanium carbide oxide film, and a zinc oxide (ZnO) -aluminum oxide (Al ₂ O ₃ ) film formed on a polyimide film is 4 or more and an average positive The reflectance was 0.15%, the lightness (L ^* ) of the film surface was 31, and blackness was increased by forming a zinc oxide (ZnO) -aluminum oxide (Al ₂ O ₃ ) film.
Further, after the preparation, it was left in the atmosphere for 2 weeks, but the color difference (ΔE ^* ab) representing the antioxidant property was calculated to be 0.6, and the color change was invisible to the naked eye.
Although it was heated at 100 ° C., 200 ° C., 270 ° C. for 30 minutes in air and treated at a temperature of 85 ° C. and a humidity of 85% RH for 500 hours, there was no change in average optical density and average regular reflectance, and color difference (ΔE ^* ab) was also in the range of 0.1 to 0.7 which was not visually recognized. In the heat resistance test and the adhesion test after the high temperature and high humidity test, the film was not peeled off. Table 3-2 summarizes the characteristics of the heat-resistant and light-shielding multilayer film.
Therefore, the produced heat-resistant light-shielding multilayer film has a complete light-shielding property, low regular reflectance, and extremely high blackness, so it can be used for camera module apertures for camera-equipped mobile phones and shutter blade materials for digital cameras. Use is useful.

(Examples 53 to 58)
The types of resin films are polyamideimide (Example 53), polyetheretherketone (Example 54), polyethylene terephthalate (Example 55), polyethylene naphthalate (Example 56), polyphenylene sulfide (Example 57), polyethersulphate. A heat-resistant light-shielding multilayer film was produced in the same manner as in Example 1 except that the material was changed to Phong (Example 58), and the type, composition, and film thickness of the metal light-shielding film, black coating film, and transparent metal compound film were the same.
The average optical density, average regular reflectance, brightness, and color difference of the produced heat-resistant light-shielding multilayer film were the same as in Example 1 as shown in Table 3-2.
In Example 55 and Example 56, the film was deformed or melted when heated at 200 ° C. or higher for 30 minutes. In Examples 53 to 58, the treatment was performed at a temperature of 85 ° C. and a humidity of 85% RH for 500 hours. However, as in Example 1, there was no change in average optical density and average regular reflectance, and color difference (ΔE ^* ab) Was 0.4, which was not visually recognized. The heat-resistant light-shielding film produced in Examples 53, 54, 57, and 58 did not peel off in the adhesion test after the heat resistance test or the high temperature and high humidity test.
Therefore, the heat-resistant light-shielding multilayer film produced in Examples 53, 54, 57, and 58 has a complete light-shielding property, low regular reflectance, and extremely high blackness. Use for shutter blades for digital cameras is useful. Moreover, the heat-resistant light-shielding multilayer film produced in Examples 55 and 56 is useful if used in an environment of 100 ° C. or lower.

(Example 59)
A 50 μm thick adhesive layer using a highly heat-resistant acrylic adhesive (trade name: 9079, manufactured by Sumitomo 3M Limited) was formed on both surfaces of the heat-resistant light-shielding multilayer film produced in Example 1, and a heat-resistant light-shielding tape was used. Produced.
Even after the heat treatment at 270 ° C. in the air, the optical density was completely light-shielding with an average optical density at a wavelength of 380 to 780 nm of 4.0 or more. The average regular reflectance was as low as 0.15%, and the average optical density and average regular reflectance did not change before and after the heat treatment, and there was no color change.

(Example 60)
A protective sheet having a slightly adhesive layer was laminated on both surfaces of the heat-resistant light-shielding multilayer film produced in Example 1. The sheet was cut into a 100 mm square sheet, and a large number of ring-shaped apertures having an outer diameter of 4 mmφ and an inner diameter of 2 mmφ having a structure in which the apertures were connected by leads at the outer periphery in a circle of 80 mmφ were produced by punching. In the punching process, after punching into a ring-shaped aperture, punching into an 80 mmφ wafer was performed, and the fine-adhesive protective sheet was peeled off to obtain a wafer on which a large number of apertures were formed.
The appearance of the aperture surface was observed with a metal microscope, but no defects such as cracks and burrs were observed.
Therefore, the manufactured heat-resistant light-shielding multilayer film can be punched into a diaphragm shape in the form of a wafer, has low surface reflection and gloss, and has no cracks or burrs due to punching. Very useful.

  The heat-resistant light-shielding multilayer film of the present invention is a shutter blade or aperture blade for a lens shutter of a digital camera or a digital video camera, a fixed aperture in a lens unit of a mobile phone with a camera or an in-vehicle monitor, Used as optical equipment parts such as diaphragm blades (also called auto iris) and heat-resistant light-shielding tape.

DESCRIPTION OF SYMBOLS 1 Resin film base material 2 Metal light-shielding film 3 Black coating film 4 Transparent metal compound film | membrane 12A Unwinding roll 12B Winding roll 13A Magnetron cathode 13B Magnetron cathode 13C Magnetron cathode 14A Target 14B Target 14C Target 15 Can roll 16 Partition

Claims (25)

  A resin film (A) having a heat resistance of 100 ° C. or higher and having a surface with an arithmetic average height Ra of 0.2 to 2.2 μm of fine irregularities is used as a base material. A metal light-shielding film (B) as a layer, a black coating film (C) as a second layer whose main component is titanium and oxygen and the O / Ti atomic ratio in the film is 0.7 to 1.4, and A heat resistant light-shielding multilayer film, wherein a third layer of a transparent metal compound film (D) is sequentially formed.   The transparent metal compound film (D) is an oxide, nitride oxide, carbide oxide, or carbonitride oxide of one or more elements selected from aluminum, titanium, silicon, zinc, indium, gallium, tin, and magnesium. The heat-resistant and light-shielding multilayer film according to claim 1, wherein   The heat-resistant light-shielding multilayer film according to claim 1 or 2, wherein the metal content of the transparent metal compound film (D) is less than 0.8 as a metal / oxygen atom number ratio.   The heat-resistant light-shielding multilayer film according to any one of claims 1 to 3, wherein the transparent metal compound film (D) has a thickness of 5 to 250 nm.   When the transparent metal compound film (D) is formed on the optical glass substrate, the parallel light transmittance at a wavelength of 380 to 780 nm is 70% or more on average, and the average regular reflectance is 20% or less. The heat-resistant and light-shielding multilayer film according to any one of claims 1 to 4, wherein   The metal light-shielding film (B) is selected from the group consisting of one or more elements selected from titanium, tantalum, tungsten, cobalt, nickel, niobium, iron, zinc, copper, aluminum, and silicon. Item 2. The heat-resistant and light-shielding multilayer film according to Item 1.   The heat-resistant light-shielding multilayer film according to claim 1, wherein the metal light-shielding film (B) is a titanium carbide film or a titanium carbide oxide film.   The carbon content of the metal light-shielding film (B) is 0.6 or more as a C / Ti atomic ratio, and the oxygen content is 0.4 or less as an O / Ti atomic ratio. The heat-resistant light-shielding multilayer film according to claim 1.   The heat-resistant light-shielding multilayer film according to claim 1, wherein the metal light-shielding film (B) has a thickness of 40 to 250 nm.   The heat resistant light-shielding multilayer film according to claim 1, wherein the black coating film (C) further contains carbon.   The heat resistant light-shielding multilayer film according to claim 1, wherein the black coating film (C) has a thickness of 50 to 250 nm.   The resin film (A) is mainly composed of one or more kinds of resins selected from polyimide, polyamideimide, polyphenylene sulfide, polyethylene naphthalate, polyethylene terephthalate, polycarbonate, aramid, polyetheretherketone, or polyethersulfone. It is a film, The heat-resistant light-shielding multilayer film in any one of Claims 1-11 characterized by the above-mentioned.   The heat-resistant light-shielding multilayer film according to claim 1, wherein the resin film (A) has a thickness of 10 to 250 μm.   A metal light-shielding film (B), a black coating film (C), and a transparent metal compound film (D) having substantially the same film thickness and the same composition on both surfaces of a resin film (A) having a heat resistance of 100 ° C. or higher. Is formed and has a symmetrical structure with respect to the resin film (A), the heat-resistant and light-shielding multilayer film according to any one of claims 1 to 13.   2. The heat-resistant light-shielding multilayer film according to claim 1, wherein an average optical density, which is an indicator of light shielding properties, is 4.0 or more at a wavelength of 380 to 780 nm and an average regular reflectance is less than 0.3%. In L ^* a ^* b ^* color system measurement (JISZ8729) standardized by CIE (International Commission on Illumination), L ^* (brightness) is 20 to 35, and color difference after being left in the atmosphere for 2 weeks (ΔE * ab) is less than 1.0, and the heat-resistant and light-shielding multilayer film according to claim 1 or 15. A resin film (A) having a fine surface irregularity with an arithmetic average height Ra of 0.2 to 2.2 μm is supplied to a sputtering apparatus,
Sputtering using a metal light shielding film target under an inert gas atmosphere, forming a metal light shielding film (B) on the resin film (A),
Next, sputtering is performed using a target for forming a black coating film under a deposition gas pressure of 1.5 Pa or more in an inert gas atmosphere, and titanium, oxygen, and carbon are mainly contained on the metal light-shielding film (B). After forming a black coating film (C) in which the O / Ti atomic ratio in the film is 0.7 to 1.4,
Sputtering using a transparent metal compound (D) forming target in an inert gas atmosphere, an oxide of one or more elements selected from aluminum, titanium, silicon, zinc, indium, gallium, tin, and magnesium, A transparent metal compound (D) which is a nitrided oxide, a carbide oxide, or a carbonitride oxide and has a metal content in the film of less than 0.8 as a metal / oxygen atom number ratio is formed. Item 17. A method for producing a heat-resistant and light-shielding multilayer film according to any one of Items 1 to 16.   The metal target, metal oxide target, metal carbide target or metal nitridation in which the transparent metal compound film (D) contains one or more elements selected from aluminum, titanium, silicon, zinc, indium, gallium, tin, and magnesium It is formed by using any one of the target targets, introducing oxygen gas and / or nitrogen gas into argon gas, and sputtering at a film forming gas pressure of 0.2 to 0.8 Pa. Item 18. A method for producing a heat-resistant multi-layer film according to Item 17.   The method for producing a heat-resistant and light-shielding multilayer film according to claim 17 or 18, wherein a film forming gas pressure when forming the metal light-shielding film (B) is 0.2 to 0.8 Pa. The metal light-shielding film (B), the black coating film (C), and the transparent metal compound film (D) on one side obtained by the method for producing a heat-resistant light-shielding multilayer film according to any one of claims 17 to 19. A heat-resistant light-shielding film comprising a laminated film formed in the order of
A metal light-shielding film (B) is formed on the other surface where the laminated film of the resin film substrate (A) is not formed by sputtering using a target for forming the metal light-shielding film (B) in an inert gas atmosphere. Forming,
Next, by sputtering using a black coating film forming target in an inert gas atmosphere, an O / Ti atomic ratio in the film containing titanium, oxygen, and carbon as main components on the metal light-shielding film (B). After forming a black coating film (C) having a thickness of 0.7 to 1.4,
An oxide of one or more elements selected from aluminum, titanium, silicon, zinc, indium, gallium, tin, and magnesium by sputtering using a transparent metal compound (D) forming target in an inert gas atmosphere; A heat resistance characterized by forming a transparent metal compound (D), which is a nitrided oxide, a carbide oxide, or a carbonitride oxide, wherein the metal content in the film is less than 0.8 as the metal / oxygen atom ratio. Manufacturing method of light-shielding multilayer film.   A diaphragm having excellent heat resistance obtained by punching the heat-resistant light-shielding multilayer film according to any one of claims 1 to 16.   The diaphragm having excellent heat resistance according to claim 21, which is used in a camera module having a wafer level chip size package (WLCSP) structure.   A shutter blade excellent in heat resistance obtained by punching the heat-resistant light-shielding multilayer film according to any one of claims 1 to 16.   A diaphragm blade for light amount adjustment excellent in heat resistance obtained by punching the heat-resistant light-shielding multilayer film according to any one of claims 1 to 16.   A heat-resistant light-shielding tape comprising an adhesive layer on one side or both sides of the heat-resistant light-shielding multilayer film according to claim 1.

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