WO2013018467A1

WO2013018467A1 - Black diamond-like carbon coating film with inclined structure, method for manufacturing same, black light shield, and shutter blade using same

Info

Publication number: WO2013018467A1
Application number: PCT/JP2012/066255
Authority: WO
Inventors: 勝史小野; 水沼　昌平
Original assignee: 住友金属鉱山株式会社
Priority date: 2011-07-29
Filing date: 2012-06-26
Publication date: 2013-02-07
Also published as: TW201309821A

Abstract

Provided is a black diamond-like carbon (DLC) coating film with an inclined structure, for enhancing the low reflectivity, black color properties, light weight, sliding properties, and water-repellent properties of a shutter blade. Also provided is a black light shield having reduced weight and excellent high-temperature/humidity characteristics, which uses a resin film or the like as a base material and has the black DLC coating film with an inclined structure as a surface layer thereof. A black diamond-like carbon (DLC) coating film (A) with an inclined structure, formed by a sputtering method and containing titanium, carbon, and oxygen, is characterized in having a structure in which the carbon content of the black DLC coating film (A) with an inclined structure is 2.0-30.0 in terms of the C/Ti atom ratio, the oxygen content is 0.8-2.2 in terms of the O/Ti atom ratio, and the C/Ti atom ratio and the O/Ti atom ratio continuously vary in the thickness direction of the film, the film thickness of the black DLC coating film (A) with an inclined structure being at least 20 nm.

Description

Diamond-like carbon gradient structure black coating film, manufacturing method thereof, black light shielding plate, and shutter blade using the same

The present invention relates to a diamond-like carbon (hereinafter sometimes referred to as DLC) gradient structure black coating film, a method for producing the same, a black light shielding plate, and a shutter blade material using the same, and more specifically, a surface of an optical member. Low-reflective, black, slidable and water-repellent diamond-like carbon (DLC) gradient structure black coating film, and black light-shielding plate using resin film and the like as a base substrate and its manufacture The present invention relates to a method and a shutter blade using the method.

In recent years, high-speed (mechanical) shutters for digital cameras have been actively developed. This is because if the shutter speed is increased, a very high-speed subject can be photographed without blur and a clear image can be obtained. In general, a shutter opens and closes by rotating and moving a plurality of blades called shutter blades, but in order to increase the shutter speed, the shutter blades are lightened so that they can be stopped and operated in a very short time, and Requires high slidability. Further, when the shutter is closed, the shutter blade has a role of blocking light by covering the front surface of a photosensitive material such as a film or an image pickup device such as a CCD or CMOS, and needs to be completely shielded from light. In addition, when a plurality of shutter blades overlap each other, the shutter blades have a low light reflectance on the blade surface to prevent leakage light between the blades, that is, high blackness. desired.

In recent years, a small-sized mechanical shutter has begun to be mounted on a lens unit so that a mobile phone having a shooting function, that is, a mobile phone with a camera, can perform high-quality shooting with high pixels. The mechanical shutter incorporated in the mobile phone is required to operate with less power than a general digital camera. For this reason, the weight reduction of the shutter blade is particularly strongly required.
Furthermore, in the manufacture of lens units for digital cameras and cellular phones, shutter blades have been used in the past because many methods have been used to fix each component using an ultraviolet curable resin such as an epoxy resin or acrylic resin. In addition to low reflectivity, blackness, and lightness, UV resistance is required to prevent deformation and discoloration even when irradiated with ultraviolet rays. If it is deformed, irregularities are formed on the surface of the blade material so that the blades collide with each other and stable sliding cannot be obtained. In addition, when the color is changed, the color of the reflected light reflected by the blade material changes, so that the imaging quality is deteriorated.

Also, there are cases where digital cameras and camera phones are used in high temperature and high humidity environments. In particular, if the shutter blades are attracted to the blade members or the peripheral members to be joined under high temperature and high humidity, the torque required for driving the blade members and the expected slidability are reduced, and the image Since quality deteriorates, water repellency is required on the surface of the blade material.

A metal thin plate, a ceramic thin plate, a glass plate, a resin plate, a resin film, or the like is generally used as the base material of the light shielding plate used for the shutter blade described above according to the required characteristics.
As the metal thin plate, a metal thin plate such as SUS, SK material, Al, Ti or the like can be used as the base material of the light shielding film. Although there is a metal thin plate itself as a light shielding plate, it has a metallic luster and 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 metal thin plate has low reflectivity and blackness, but is not suitable for increasing the shutter speed because the metal thin plate is heavy. Patent Document 1 discloses a light shielding material in which a hard carbon film is formed on the surface of a metal blade material such as an aluminum alloy.
However, since a metal plate is used, a high shutter speed cannot be expected. Moreover, even if a hard carbon film is formed on the surface, depending on the film thickness and composition, the low reflection characteristic of the light shielding material cannot be realized, and the generation of stray light due to reflected light may be unavoidable. When the light shielding plate using the metal thin plate as a base material is used as a shutter blade material, since the weight is large, the torque of the drive motor that drives the blade increases, the power consumption increases, and the shutter speed cannot be increased. Problems such as generation of noise due to contact between blades occur.

On the other hand, a light shielding plate using a resin film as a base material has also been proposed. Patent Document 2 proposes a light-shielding plate using a matted resin film to reduce surface reflection, and a film-shaped light-shielding plate with matteness formed by forming a large number of fine uneven surfaces. ing.
Patent Document 3 proposes a light-shielding film in which a thermosetting resin containing a matte paint is coated on a resin film. However, these only reduce the reflection of the surface by processing the resin film itself or adding a matting agent, and are not considered to prevent the influence of stray light due to reflection from the light shielding blade.

For light shielding plates using a resin film as a base material, polyethylene terephthalate (PET) is often used as a base material because of its low specific gravity, low cost, and flexibility. In addition, PET films that contain black fine particles such as carbon black and titanium black and have reduced transmittance are widely used. For example, Patent Document 4 proposes coating a base material with a coating film containing acicular or granular fine material such as titanium oxide.

However, in the case of a high-speed shutter blade, it is necessary to reduce the thickness of the film in accordance with the increase in the sliding speed. However, in the case of a black PET material containing black fine particles, if the thickness of the film is reduced (for example, 38 μm or less) It cannot exhibit sufficient light shielding properties and cannot be used for shutter blades.

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 a compound of a specific element satisfying the properties of conductivity, lubricity and scratch resistance, etc. A light shielding blade material obtained by sequentially laminating thin films (protective films) is proposed. Here, there is no mention of low reflectivity and blackness, which are characteristics required for recent light-shielding blades. Moreover, the effect of the protective film shows only the effect of carbon related to scratch resistance, and does not show the specific film thickness and composition.

Patent Document 6 proposes a shutter blade material having a diamond-like carbon film (DLC) formed on the surface of a magnesium alloy and having improved rigidity and lubricity. The characteristics of diamond-like carbon depend greatly on the production method and the abundance ratio of sp2-bonded carbon and sp3-bonded carbon. Here, it does not show an optimum diamond-like carbon production method and composition that can provide high rigidity and high lubricity.
As described above, there are coating film materials for reducing the reflectance and blackening of the surfaces of optical components such as shutter blades, but none of them has been found to have excellent slidability and water repellency.

Under such circumstances, a metal thin plate or resin film having a relatively small weight such as SUS, SK material, Al, Ti or the like is used as the base material, and the torque and power consumption of the drive motor for driving the blades can be suppressed, and the shutter There is a need for a shutter blade material that can increase speed, has no noise due to contact between the blades, and has both sufficient light-shielding property, low reflection property, and water repellency in the visible range.

Japanese Patent Laid-Open No. 2-116837 JP-A-1-120503 JP 4-9802 A Japanese Patent Laid-Open No. 2002-40512 JP 2006-138974 A JP 2010-134159 A

The present invention provides a coating material capable of improving the low reflectivity, blackness, lightness, slidability, and water repellency of a shutter blade, that is, a diamond-like carbon (DLC) gradient structure black coating film. With the goal. Furthermore, it aims at providing the black light-shielding board excellent in the high temperature high-humidity characteristic which made the base substrate the resin film etc. which formed this coating film in the surface layer, and was reduced in weight.

As a result of searching for coating film materials capable of improving the slidability and water repellency, the present inventors have made the surface of optical components such as shutter blades have high light-shielding properties, low reflectance, and blackening. A structure in which oxygen and carbon are the main components, the amount of titanium (C / Ti atom number ratio) and the amount of oxygen (O / Ti atom number ratio) are in specific ranges, and the titanium amount continuously changes in the film thickness direction. Before forming the diamond-like carbon (DLC) gradient structure black coating film, the above-mentioned performance can be achieved by forming a black light-shielding plate in which a metal light-shielding film is further formed and laminated on the substrate surface. The inventors have found that the characteristics are not impaired even in a high humidity environment, and have completed the present invention.

That is, the first invention of the present invention is a diamond-like carbon gradient structure black coating film (A) containing titanium, carbon, and oxygen, formed by sputtering, and this diamond-like carbon gradient structure black coating film. The carbon content of the coating (A) is 2.0 to 30.0 as the C / Ti atomic ratio, the oxygen content is 0.8 to 2.2 as the O / Ti atomic ratio, and C / Ti The diamond-like carbon gradient structure black coating film has a structure in which the atomic ratio and the O / Ti atomic ratio are continuously changed in the film thickness direction, and the film thickness is 20 nm or more.

In the second invention of the present invention, the oxygen and titanium contents increase in the film thickness direction from the film surface on the sputtering side of the diamond-like carbon gradient structure black coating film (A) in the first invention, and the carbon content Is a diamond-like carbon gradient structure black coating film characterized by a decrease in

According to a third aspect of the present invention, there is provided a diamond-like carbon gradient structure black, wherein the diamond-like carbon gradient structure black coating film (A) in the first and second inventions has a thickness of 20 to 200 nm. It is a coating film.

In the fourth invention of the present invention, the carbon composition in the diamond-like carbon gradient structure black coating film (A) in the first to third inventions is a mixture of sp2 bonded carbon and sp3 bonded carbon. A diamond-like carbon gradient structure black coating film characterized by the following.

A fifth aspect of the present invention is a diamond-like carbon (DLC) characterized in that the diamond-like carbon gradient structure black coating film according to the first to fourth aspects has a static contact angle with respect to water of 90 ° or more. ) An inclined structure black coating film.

The sixth invention of the present invention is the diamond-like carbon gradient structure black coating, wherein the dynamic friction coefficient of the diamond-like carbon gradient structure black coating film in the first to fifth inventions is 0.1 or less. It is a membrane.

In the seventh invention of the present invention, the arithmetic average height (Ra) in the region of 1 μm × 1 μm, measured with an atomic force microscope of the diamond-like carbon gradient structure black coating film in the first to sixth inventions, It is a diamond-like carbon gradient structure black coating film characterized by being 0.8 nm or more.

In the eighth invention of the present invention, the parallel light transmittance at a wavelength of 380 to 780 nm of the diamond-like carbon gradient structure black coating film formed on the glass substrate according to the first to seventh inventions by sputtering is 20 on average. A diamond-like carbon gradient structure black coating film characterized in that it is ˜50%.

The ninth aspect of the present invention is a film formation of 1.5 Pa or more using a sputtering target selected from a combination of a titanium sintered body and a carbon sintered body, or a combination of a titanium carbide sintered body and a carbon sintered body. A diamond-like carbon gradient structure black coating film is formed by sputtering with a gas pressure to form a diamond-like carbon gradient structure black coating film on a substrate.

A tenth invention of the present invention is a dual magnetron cathode using a target selected from the combination of the titanium sintered body and the carbon sintered body or the combination of the titanium carbide sintered body and the carbon sintered body in the ninth invention. Alternatively, a diamond-like carbon gradient structure black coating film is formed by sputtering with a double magnetron cathode to form a diamond-like carbon gradient structure black coating film on a substrate.

The eleventh aspect of the present invention is a composition comprising a target selected from a combination of a titanium sintered body and a carbon sintered body or a combination of a titanium carbide sintered body and a carbon sintered body in the ninth to tenth inventions. Oxygen gas is not introduced as a film formation gas into the film, and an inert gas mainly containing argon or helium is introduced to form a sputtering film. Oxygen contained in the sintered body or residual gas in the film formation chamber It is a method for producing a diamond-like carbon gradient structure black coating film characterized by incorporating either oxygen or both into the film.

The twelfth aspect of the present invention is a black light shielding plate comprising a base material (B), a metal light shielding film (C), and a black coating film, wherein the base material (B) has fine irregularities on the surface. A metal light-shielding film (C) having a film thickness of 40 nm or more provided on at least one surface of the base material (B), and a metal light-shielding film (C). A black light shielding plate, wherein the black coating film provided on the surface of C) is the diamond-like carbon gradient structure black coating film (A) of any one of the first to eighth inventions.

In a thirteenth aspect of the present invention, the base material (B) in the twelfth aspect is a thin metal plate of stainless steel, SK (carbon steel), Al, Ti, alumina, magnesia, silica, zirconia ceramic thin plate, glass plate, The black light-shielding plate is any one selected from a resin plate and a resin film.

In a fourteenth aspect of the present invention, the resin film according to the thirteenth aspect is a polyimide, polyamideimide, polyetheretherketone, polyethylene terephthalate, polyphenylene sulfide, polyethylene naphthalate, polyethersulfone having a thickness of 5 to 200 μm, The black light-shielding plate is any one selected from polycarbonate.

In a fifteenth aspect of the present invention, the metal light-shielding film (C) in the twelfth to fourteenth aspects is selected from titanium, tantalum, tungsten, cobalt, nickel, niobium, iron, zinc, copper, aluminum, and silicon. It is a black light shielding plate characterized by being a metal material mainly composed of one or more kinds of elements.

A sixteenth aspect of the present invention is a black light shielding plate, wherein the metal light shielding film (C) in the twelfth to fifteenth aspects is any one of a titanium film, a titanium carbide film, and a titanium carbide oxide film. is there.

According to a seventeenth aspect of the present invention, the black light shielding plate according to the twelfth to sixteenth aspects has the same film thickness and the same composition on both surfaces of any one of a resin film, a resin plate, a metal thin plate, and a ceramic thin plate. A metal light-shielding film (C), and a diamond-like carbon gradient structure black coating film (A) having the same film thickness and the same composition on the surface of the metal light-shielding film (C). It is a black light shielding plate characterized by having a symmetrical structure with a center.

According to an eighteenth aspect of the present invention, the black light shielding plate according to the twelfth to seventeenth aspects is an arithmetic average of the diamond-like carbon gradient structure black coating film (A) formed on the surface of the metal light shielding film (C). A black having an average regular reflectance of 0.8% or less on the surface of the diamond-like carbon gradient structure black coating film (A) at a height Ra of 0.2 to 0.7 μm and a wavelength of 380 to 780 nm It is a light shielding plate.

According to a nineteenth aspect of the present invention, the brightness (L ^* ) of the black light shielding plate in which the diamond-like carbon gradient structure black coating film (A) is provided on the surface of the metal light shielding film (C) of the twelfth to eighteenth aspects ^. ) Is a black shading plate characterized by being 25-45.

According to a twentieth aspect of the present invention, a colored resin film is used as a base material (B), the metal light-shielding film (C) is provided on at least one surface thereof, and the metal light-shielding film (C) is provided on the surface thereof. A black light shielding plate provided with the diamond-like carbon gradient structure black coating film (A) according to any one of the first to tenth aspects, wherein the diamond-like carbon gradient structure black coating film (A) has a thickness of 20 nm or more and has a wavelength. The black light-shielding plate is characterized in that the average regular reflectance on the surface of the black light-shielding plate at 380 to 780 nm is 1% or less.

21st invention of this invention is a black light-shielding board characterized by the colored resin film in 20th invention having surface unevenness | corrugation.

According to a twenty-second aspect of the present invention, there is provided a black light shielding plate, wherein the diamond-like carbon gradient structure black coating film (A) in the twentieth and twenty-first aspects has a thickness of 20 to 200 nm.

A twenty-third aspect of the present invention is a black light-shielding plate, wherein the metal light-shielding film (C) in the twentieth to twenty-second aspects has a thickness of 20 to 200 nm.

According to a twenty-fourth aspect of the present invention, a metal light-shielding film (C) is provided on the colored resin film in the twentieth to twenty-third aspects, and a diamond-like carbon gradient structure black coating is provided on the surface of the metal light-shielding film (C). The black light shielding plate is characterized in that the lightness (L ^* ) of the black light shielding plate obtained by forming a film is 25 to 45.

According to a twenty-fifth aspect of the present invention, there is provided a black light shielding plate, wherein the colored resin film according to the twentieth to twenty-fourth aspects has a thickness of 20 to 200 μm.

The twenty-sixth invention of the present invention is a shutter blade obtained by punching the black light shielding plate in the twelfth to twenty-fifth inventions.

The diamond-like carbon (DLC) gradient structure black coating film of the present invention is a diamond-like carbon (DLC) thin film mainly composed of titanium, carbon, and oxygen formed by sputtering, and has a carbon content of C / C. Ti atomic ratio is 2.0-30.0, oxygen content is O / Ti atomic ratio 0.8-2.2, and C / Ti atomic ratio, O / Ti atomic ratio Is a diamond-like carbon (DLC) gradient structure black coating film that continuously changes in the film thickness direction, so that coating of optical members requiring high light-shielding properties, low reflectivity, blackness, slidability, and water repellency Useful as a material. Furthermore, since it has high water repellency under high temperature and high humidity, it is extremely useful as a coating material for shutter blades of digital cameras and camera-equipped mobile phones.

Further, the light shielding plate in which the diamond-like carbon (DLC) gradient structure black coating film of the present invention is formed on a resin film is lighter than a conventional light shielding plate based on a thin metal plate because the resin film is used as a substrate. Excellent in properties. Even if a diamond-like carbon (DLC) gradient structure black coating film is formed as a coating film, it does not impair low reflectivity, blackness, and light-shielding properties, so it is used as a shutter blade material for digital cameras and mobile phones with cameras. Industrial value is extremely high.

Furthermore, the black light-shielding plate of the present invention is also effective for shutter blades of high-speed shutters, because even if the thickness of the resin film substrate is reduced to 38 μm or less in order to reduce weight, sufficient light-shielding properties are not impaired. Therefore, the drive motor can be miniaturized, and there are advantages such as the miniaturization of the mechanical shutter.

It is the schematic which shows the cross section of the black light-shielding board of this invention which formed the metal light-shielding film and the diamond-like carbon (DLC) gradient structure black coating film in the single side | surface of the resin film. It is the schematic which shows the cross section of the black light shielding board of this invention which formed the metal light shielding film and the diamond-like carbon (DLC) inclination structure black coating film on both surfaces of the resin film. It is the schematic which shows the cross section of the black light-shielding board of this invention which formed the metal light-shielding film and the diamond-like carbon (DLC) gradient structure black coating film in the single side | surface of a coloring base material. It is the schematic which shows the cross section of the black light-shielding board of this invention which formed the metal light-shielding film and the diamond-like carbon (DLC) gradient structure black coating film on both surfaces of the coloring base material. It is a schematic diagram which shows an example of the winding-type sputtering apparatus used in manufacturing the black light-shielding plate of this invention. 2 is a photograph of the surface of a diamond-like carbon (DLC) gradient structure black coating film obtained in Comparative Example 1 observed with an AFM. 2 is a photograph of the surface of a diamond-like carbon (DLC) gradient structure black coating film obtained in Example 1 observed with an AFM.

Hereinafter, the diamond-like carbon (DLC) gradient structure black coating film of the present invention, the black light shielding plate, and its application will be described with reference to the drawings.

1. Diamond-like carbon (DLC) gradient structure black coating film (A)
The diamond-like carbon (DLC) gradient structure black coating film of the present invention is mainly composed of titanium, carbon, and oxygen, and has an oxygen content of 0.8 to 2.2 in terms of the number of O / Ti atoms. The amount is 2.0 to 30.0 as the C / Ti atomic ratio, and the C / Ti and O / Ti atomic ratios are continuously changed in the film thickness direction.

When the carbon content is less than 2.0 in terms of the C / Ti atomic ratio, the diamond-like carbon (DLC) gradient structure black coating film has a yellowish or brown color, and the low reflectivity and blackness are impaired. It will be. Even when the C / Ti atomic ratio exceeds 30.0, the color of the film is yellow or brown, which is not preferable because low reflectivity and blackness are impaired.

Further, when the oxygen content is less than 0.8 in terms of the O / Ti atomic ratio, the light transmittance of the film is low and the light blocking property due to light absorption is increased, while the blackness is impaired and low reflectivity is obtained. I can't. When the O / Ti atomic ratio exceeds 2.2, the water repellency is excellent, but the light transmittance is high, the film color is yellow or brown, and the blackness is inferior.

The C / Ti atomic ratio and the O / 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 lot of oxygen, it is removed by sputtering to a depth of about 10 nm in a vacuum, and then the C / Ti atomic ratio and O / Ti atomic ratio in the film are quantified if measured afterwards. Can be
Even with the film composition as described above, the low reflectivity and blackness of the film depend on the film thickness, and when the film thickness is 20 nm or more, the film absorbs light sufficiently, resulting in low reflectivity and blackness. Can demonstrate its sexuality. On the other hand, the film thickness capable of exhibiting slidability and water repellency is 20 nm or more, preferably 50 nm or more.

Also, the C / Ti atomic ratio and the O / Ti atomic ratio change continuously in the film thickness direction of the diamond-like carbon (DLC) gradient structure black coating film. Black coating with C / Ti atom number ratio and O / Ti atom number ratio on the film surface side being larger than the inside of the film, and the outermost surface of the film is a composite diamond-like carbon (DLC) containing titanium, oxygen and carbon A membrane is obtained. Since titanium and oxygen are contained on the outermost surface of the film, water repellency (contact angle with water of 90 ° or more) and slidability (dynamic friction coefficient of 0.10 or less) that cannot be obtained with only a diamond-like carbon (DLC) thin film Can be granted.

The C / Ti atomic ratio and the O / Ti atomic ratio change continuously in the film thickness direction of the diamond-like carbon (DLC) gradient structure black coating film. A structure having no interface due to a difference in composition can be obtained, and the adhesion to the base film is excellent. In addition, an extinction coefficient and a refractive index difference are generated in the diamond-like carbon (DLC) gradient structure black coating, and the effect of preventing light reflection on the film surface is obtained, compared with the case where a film having a single film composition is formed. Can also be reduced in reflection.

The diamond-like carbon (DLC) gradient structure black coating film of the present invention preferably has surface unevenness. As for the surface irregularity, the arithmetic average height (Ra) in the region of 1 μm × 1 μm of the black coating film surface measured by an atomic force microscope is 0.8 nm or more, preferably 2.0 nm or more. Thereby, reflected light is scattered, low reflectivity can be ensured, and it becomes useful as an optical member.

The diamond-like carbon (DLC) gradient structure black coating film of the present invention 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 diamond-like carbon. (DLC) It is also included in the gradient structure black coating film. Thus, even if the above elements are included in the diamond-like carbon (DLC) gradient structure black coating film, the characteristics of the black coating film may not be impaired.

The diamond-like carbon (DLC) gradient structure black coating film of the present invention is a metal thin plate of SUS, SK, Al, Ti, a ceramic thin plate, a glass plate, a resin plate, whose main component is a metal oxide of alumina, magnesia, or silica, Alternatively, it can be made low-reflective and black when formed on a metal light-shielding film formed on the surface of a substrate such as a resin film, and is effectively used as a black coating film with excellent slidability, water repellency and UV resistance can do.

Further, when the surface of the base material forming the diamond-like carbon (DLC) gradient structure black coating film is made uneven, the surface irregularity of the diamond-like carbon (DLC) gradient structure black coating film can be further increased, A matte effect can also be obtained.
When the base material is a thin metal plate, a ceramic thin plate or glass plate mainly composed of a metal oxide such as alumina, magnesia, or silica, the specified surface irregularities can be obtained by etching, nanoimprinting, or mat processing using shot material. Can be formed.
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. When a resin film or a resin plate is used as a base material, it is effective to make the base material surface uneven by the above method.

2. Method for forming black coating film The method for forming the diamond-like carbon (DLC) gradient structure black coating film of the present invention is not particularly limited, and is a vacuum deposition method, an ion beam assisted deposition method, a gas cluster ion beam assisted deposition method, Ion plating method, ion beam sputtering method, magnetron sputtering method, bias sputtering method, ECR (Electron Cyclotron Resonance) sputtering method, radio frequency (RF) sputtering method, thermal CVD (Chemical Vapor Deposition) method, plasma CVD method, photo CVD method A known method such as the above can be appropriately employed. Especially, it is preferable to manufacture by a sputtering method.
By manufacturing by a sputtering method, a diamond-like carbon (DLC) gradient structure black coating film having high adhesion can be formed on a substrate.

Although the manufacturing apparatus by sputtering method is not specifically limited, For example, the winding type sputtering apparatus shown in FIG. 5 can be used.
First, a roll-shaped resin film substrate 11 is set on an unwinding roll 12, and after the inside of the vacuum chamber 14 in the film forming chamber is evacuated by a vacuum pump 13 such as a turbo molecular pump, the film is unloaded from the unwinding roll 12. In the middle, 11 is passed through the surface of the cooling can roll 15 and taken up by the take-up roll 16. Two magnetron cathodes 17 are installed on the opposite side of the surface of the cooling can roll 15, and a target 18 as a film raw material is attached to each cathode. In the case where the targets 18 installed on the two magnetron cathodes 17 are a titanium carbide sintered body target and a carbon sintered body target, first, on the titanium carbide sintered body target with respect to the transport direction of the resin film substrate 11, A film is formed, and then a film is formed on the carbon sintered compact target. Note that the film transport unit including the unwinding roll 12 and the winding roll 16 is separated from the vacuum chamber 14 of the film forming chamber by a partition wall 19.

Usually, sputtering film formation is often performed at a sputtering gas pressure of 0.2 to 0.8 Pa. Under such conditions, the surface becomes relatively flat as shown in FIG. The diamond-like carbon (DLC) gradient structure black coating film of the present invention uses a titanium sintered body and a carbon sintered body, or a titanium carbide sintered body and a carbon sintered body target. It is manufactured by performing sputtering film formation under gas pressure, and as shown in FIG. 7, high-quality titanium oxide having the above composition and structure, or diamond-like carbon combined with titanium carbide oxide ( DLC) gradient structure black coating film. Further, by forming protrusions on the surface, low reflection can be achieved on the film surface by the light scattering effect.

As a method of continuously changing titanium, oxygen, and carbon in the film thickness direction, a dual magnetron cathode is used for the sputtering cathode, and the film gas pressure is changed to incline the composition with respect to the film thickness direction. A structure with a mark is obtained. This dual magnetron cathode is arranged so that the extended surfaces of the surface of the target of the two magnetrons are located on substantially the same plane.

In the sputtering method using a dual magnetron cathode, AC power of a rectangular pulse whose polarity is switched with a period of about 1 to 100 kHz is applied between these two magnetrons, and a negative potential is applied among the two magnetrons. On the surface of the raw material target attached to the magnetron (working as a cathode), positively charged ions are accelerated by an electric field and collide, and atoms on the surface of the raw material are knocked out (sputtering). It is discharged into the device space to form a desired thin film on the substrate.
Further, the composition can be adjusted by using a double magnetron cathode and adjusting the sputtering power at each cathode.

That is, if sputtering film formation is performed at a film forming gas pressure of 1.5 Pa or more using a titanium sintered body and a carbon sintered body target, and a titanium carbide sintered body and a carbon sintered body, Ti, O, and C are changed. The main component is C / Ti atomic number ratio of 2.0 to 30.0, O / Ti atomic ratio is 0.8 to 2.2, and the atomic ratio is continuous in the film thickness direction. The structure can be obtained and a diamond-like carbon (DLC) gradient structure black coating film having protrusions on the film surface can be obtained.
Furthermore, by setting the film forming gas pressure to 1.5 Pa or more, fine protrusions are formed on the film surface, so that the contact area with water droplets under high temperature and high humidity is reduced, and water repellency can be expressed.

As described above, a sintering aid is often added to improve the sintering density of a sputtering target used as a raw material for sputtering film formation.
The sintered compact target used when forming the diamond-like carbon (DLC) gradient structure black coating film of the present invention includes Fe, Ni, Co, Zn, Cu, Mn, In, Sn, Nb, Ta, and the like. An element can be added as a sintering aid as long as the characteristics of the black coating film of the present invention are not impaired.

In the present invention, the diamond-like carbon (DLC) gradient structure black coating film is formed by using only an inert gas mainly containing argon or helium without supplying oxygen gas as a film forming gas. It can also be manufactured. 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 the 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 content in the sintered body target and the oxygen in the residual gas in the sputtering film forming chamber are too small, that is, in the sputtering film forming performed at a normal film forming gas pressure of 0.2 to 0.8 Pa, the film is sufficient. In this case, oxygen is not contained, and in that case, the film forming gas pressure is set to 1.5 Pa or more, so that the black coating film can be obtained by sufficiently containing oxygen.

The film formation method using oxygen contained in the sintered compact target and oxygen in the residual gas in the sputtering film formation 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.

The film-forming temperature differs depending on the type of substrate and is difficult to specify. However, if it is a metal thin plate, a ceramic thin plate or glass plate mainly composed of a metal oxide such as alumina, magnesia, or silica, it is 400 ° C. or less, for example. If it is a resin film, it can be 300 degrees C or less, for example.

3. Substrate (B)
As the substrate (B), a metal thin plate of stainless steel, SK (carbon steel), Al, Ti, a ceramic thin plate such as alumina, magnesia, silica, zirconia, a glass plate, a resin plate, or a resin film can be used.
Among them, it is preferable to use a resin film in order to realize a lightweight black light shielding plate. The resin film is preferably one kind selected from polyimide, polyamideimide, polyetheretherketone, polyethylene terephthalate, polyphenylene sulfide, polyethylene naphthalate, polyethersulfone, and polycarbonate.

The thickness of the resin film is preferably 5 to 200 μm, more preferably 10 to 150 μm, and most preferably 20 to 125 μm.
A resin film thinner than 5 μm is not preferred 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 200 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, which is inappropriate for some applications.

4). Metal light shielding film (C)
The metal light-shielding film is formed on one side or both sides of the substrate, and contains one or more elements selected from titanium, tantalum, tungsten, cobalt, nickel, niobium, iron, zinc, copper, aluminum, or silicon. A metal material having a main component 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 be used. 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 is increased. Further, the titanium carbide oxide film can be used as a metal light shielding film having excellent heat resistance.

The metal light-shielding film is formed by sputtering and may be formed under a gas pressure generally used such as 0.2 to 0.8 Pa. In addition to Ar gas, Ar gas in which oxygen is slightly mixed may be used as the sputtering gas as long as the characteristics of the black light shielding plate can be satisfied.
In general, the bond between an organic resin film and an inorganic metal film is weak. The same applies when the metal light-shielding film of the present invention is formed on the surface of the resin film. 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.

5. Black light shielding plate The structure of the black light shielding plate of the present invention is shown in FIGS. On one side or both sides of the substrate 1 selected from a resin film, a resin plate, a metal thin plate, or a ceramic thin plate, a metal light-shielding film 3 having a film thickness of 40 nm or more and the diamond-like carbon (DLC) gradient structure black coating film 2 are sequentially formed. It is a formed structure. Here, this is referred to as a first black light shielding plate.

Further, in the black light shielding plate of the present invention, the metal light shielding film 3 having a film thickness of 20 nm or more and the diamond-like carbon (DLC) gradient structure black coating film 2 are formed on one surface or both surfaces of the coloring substrate 1a. Of the structure made. The structure is shown in FIGS. Hereinafter, this is referred to as a second black light shielding plate.

By having such a structure, the average optical density in the visible region, that is, in the wavelength range of 380 to 780 nm is larger than 4.0, and the average regular reflectance on the surface of the black coating film in the wavelength range of 380 to 780 nm is 0.8% or less. An optical member can be realized. When the average optical density is greater than 4.0, the transmittance is almost zero, indicating complete light shielding properties.
Here, the optical density (OD) is a function of transmittance: T (%) represented by the following formula (1). The regular reflectance of the surface of the black coating film represents the reflectance of light reflected from the surface at an angle equal to the incident angle of incident light according to the law of reflection.

Hereinafter, the first black light shielding plate and the second black light shielding plate will be described in detail.
(1) First black light shielding plate In the first black light shielding plate of the present invention, a resin film, a resin plate, a metal thin plate, a ceramic thin plate, or the like is selected as the substrate. Among these, a resin film is preferable. Examples of the resin film include polyimide (PI), polyamideimide (PAI), polyetheretherketone (PEEK), polyethylene terephthalate (PET), polyphenylene sulfide (PPS), polyethylene naphthalate (PEN), polyethersulfone ( A film made of one or more materials selected from PES) and polycarbonate (PC), and a film having an acrylic hard coat on the surface of these films can be used.

Since these resin films generally have light transmission properties, a metal light-shielding film having a film thickness of 40 nm or more must be formed on the surface in order to have complete light-shielding properties. The thickness of the metal light shielding film is preferably 40 to 200 nm, more preferably 70 to 150 nm. If the film thickness is greater than 200 nm, it takes a long time to form the metal light-shielding film, which is not preferable because the manufacturing cost increases or the necessary film forming material increases and the material cost increases.

After forming the metal light shielding film, it is necessary to form the diamond-like carbon (DLC) gradient structure black coating film of the present invention. As a result, it is possible to realize a black light-shielding plate that is excellent in lightness and has sufficient light-shielding properties and blackness, low reflectivity, slidability, water repellency, and ultraviolet resistance. The film thickness of the diamond-like carbon (DLC) gradient structure black coating film formed on such a substrate is 20 nm or more. Furthermore, 40 nm or more, 100 nm or more are preferable, More preferably, it is 150 nm or more.
When the film thickness of the diamond-like carbon (DLC) gradient structure black coating film is less than 20 nm, the average optical density at wavelengths of 380 to 780 nm is greater than 4.0, and complete light-shielding properties can be obtained, but the diamond-like carbon (DLC) gradient The average regular reflectance on the surface of the structural black coating film exceeds 5%, and the reflectance becomes high. On the other hand, when the film thickness exceeds 200 nm, a completely light-shielding black coating film can be obtained, but there arises a problem that the sputtering time becomes long and the cost becomes high.

Further, the brightness (hereinafter referred to as L ^* ) of the black light shielding plate in which the diamond-like carbon (DLC) gradient structure black coating film is formed on the surface of the metal light shielding film is preferably 25 to 45, more Preferably it is 40 or less.
Here, the L ^* value represents the lightness (monochrome degree) represented by the CIE color system of the color, is obtained from the spectral reflectance in the visible light range, and in order to make the L ^* value less than 25, Since the film thickness of the diamond-like carbon (DLC) gradient structure black coating film exceeds 200 nm, the blackness becomes higher, the reflection can be reduced, and complete light-shielding properties can be obtained, but the sputtering time becomes longer, The problem of high costs arises. On the other hand, when the L ^* value exceeds 45, the state is opposite to that described above, the blackness is insufficient, and the regular reflectance on the surface of the diamond-like carbon (DLC) gradient structure black coating film is increased. Problems arise and are not preferred.

Further, when the resin film has surface unevenness and unevenness is generated on the surface of the diamond-like carbon (DLC) gradient structure black coating film, the regular reflectance can be reduced, that is, the effect of matting can be brought about. Therefore, it becomes a preferable optical member. In particular, when the surface roughness (arithmetic average height Ra) of the black coating film is 0.2 to 0.7 μm, the average regular reflectance of the black coating film surface at a wavelength of 380 to 780 nm is 0.8% or less. It is preferable because a black shading plate with very low reflection can be realized. Here, the arithmetic average height Ra 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 calculated. It is a value obtained by adding up and averaging.

The irregularities on the surface of the base material can be formed into predetermined irregularities by nanoimprinting 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. When forming a metal light-shielding film using a resin film as a base material, it is effective to make the surface of the resin film uneven by the above method.

Further, in the black light shielding plate of the present invention, when a resin film is used as the substrate, the resin film is soft, and thus is easily deformed by the influence of the stress of the film formed on the surface. In order to avoid this, it is effective to form films having the same configuration and the same film thickness on both sides of the resin film symmetrically on the film. In other words, after forming a metal light-shielding film with the same composition and the same film thickness on both surfaces of the resin film, the diamond-like carbon (DLC) gradient structure black coating with the same composition and the same film thickness on both surfaces (on the metal light-shielding film) A black light shielding plate obtained by forming a film is preferable because it is less deformed.

(2) Second black light-shielding plate Next, the second black light-shielding plate of the present invention is a metal light-shielding film having a thickness of 20 nm or more on one side or both sides of a colored resin film as a base material 1. The diamond-like carbon (DLC) gradient structure black coating film 2 is formed on the surface of the metal light-shielding film.

The colored resin film is preferably colored black, brown or black brown. Examples of the colored resin film include polyimide (PI), polyamideimide (PAI), polyetheretherketone (PEEK), polyethylene terephthalate (PET), polyphenylene sulfide (PPS), polyethylene naphthalate (PEN), and polyethersulfone. (PES) A film composed of one or more materials selected from polycarbonate (PC) is used as a base material, and black particles such as carbon black, titanium black, and aniline black are contained inside to reduce transmittance. Film can be used.

Further, when the surface of the colored resin film is made uneven, the surface unevenness of the diamond-like carbon (DLC) gradient structure black coating film is further increased, and a matte effect can be obtained.
The colored resin film preferably has a light transmittance of 1% or less at a wavelength of 380 to 780 nm, more preferably 0.1% or less.

The thickness of the colored resin film is preferably in the range of 20 to 200 μm, more preferably 30 to 150 μm, and most preferably 50 to 125 μm. A colored resin film thinner than 20 μm is not preferable because it has poor handling properties and is difficult to handle, is susceptible to surface defects such as scratches and creases, and has low rigidity. If the colored resin film is thicker than 200 μm, it is not preferable because a plurality of light shielding blades cannot be mounted on a shutter blade device that is becoming smaller in size, and it becomes unsuitable depending on the application.

Further, since the colored resin film is not transparent, the light transmittance at a wavelength of 380 to 780 nm in the visible light region is lower than that of a transparent resin plate or a transparent resin film having high transparency, and the metal formed on the substrate. The film thickness of the light shielding film and the diamond-like carbon (DLC) gradient structure black coating film can be made thinner than that of the first black light shielding plate.

Therefore, the thickness of the metal light-shielding film formed on the colored resin film is preferably in the range of 20 to 200 nm, more preferably 30 to 100 nm. When the thickness of the metal light-shielding film is less than 20 nm, the optical density at a wavelength of 380 to 780 nm of the black light-shielding plate is 4 even when the diamond-like carbon (DLC) gradient structure black coating film formed on the metal light-shielding film is formed with a thickness of 200 nm. The total light shielding property is lost. If it exceeds 200 nm, the sputtering time becomes very long due to the thick film thickness, which is not preferable in terms of production cost.

The film thickness of the diamond-like carbon (DLC) gradient structure black coating film is preferably in the range of 20 to 200 nm, more preferably 50 to 150 nm. When the thickness of the black coating film is 20 nm or less, the lightness (L ^* value) of the black light-shielding plate is increased even when a colored resin film having a light transmittance of 380 to 780 nm and a light transmittance of 0.1% or less is used. On the other hand, when the film thickness exceeds 200 nm, the lightness (L ^* value) of the black light-shielding plate is very low, but the film formation rate of the diamond-like carbon (DLC) gradient structure black coating film is low, so the sputtering time. However, the manufacturing cost increases, and as a manufacturing problem, the processing start time of one batch is shifted from batch to batch, and stable routineization cannot be performed.

The L ^* value of a black light shielding plate formed by forming a metal light shielding film and a diamond-like carbon (DLC) gradient structure black coating film on a colored resin film is preferably 25 to 45, more preferably 25 to 45. 40. When the L ^* value of the black light-shielding plate is less than 25, the blackness becomes higher and the reflection is reduced and complete light-shielding properties are obtained, but the film thickness of the black coating film exceeds 200 nm. Therefore, the problem that sputtering time becomes long and cost becomes high arises. On the other hand, when the L ^* value exceeds 45, the blackness is insufficient, and there is a problem that the regular reflectance on the surface of the diamond-like carbon (DLC) gradient structure black coating film increases, which is not preferable.

6). Use of black coating film or black light shielding plate The diamond-like carbon (DLC) gradient structure black coating film of the present invention can be applied as a surface coating film of an optical member, and the black light shielding plate does not cause end face cracks. It can be used as a shutter blade for digital cameras and digital video cameras by punching into a specific shape.
The present invention is described in detail below using examples.

[Sputtering target]
Titanium metal, titanium carbide, and carbon target were each prepared by hot press sintering using powder. Furthermore, metal targets such as a NiTi target (containing 3 wt% Ti), a Cu target, and an Al target were also prepared using the melt casting method.

[Preparation of diamond-like carbon (DLC) gradient structure black coating film]
Metallic titanium (purity 4N, 64 × 600 × 6 mmt) and carbon sintered body target (purity 4N, 64 × 600 × 6 mmt), or titanium carbide (purity 2N, 64 × 600 × 6 mmt) and carbon sintered body target Was used to prepare a diamond-like carbon (DLC) gradient structure black coating film by dual magnetron sputtering or double magnetron sputtering.
The composition of the membrane was adjusted by changing the deposition gas pressure in the case of a dual magnetron cathode and changing the input power and gas pressure at each cathode in the case of a double magnetron cathode. A diamond-like carbon (DLC) gradient structure black coating film by sputtering was produced by the following procedure.

The sputtering target was attached to a dual magnetron cathode or a double magnetron cathode of a take-up magnetron sputtering apparatus, and a substrate was attached so as to face the target. In addition, a titanium metal target and a carbon sintered compact target, or a titanium carbide sintered compact target and a carbon sintered compact target are arrange | positioned so that sputtering by a carbon sintered compact target may be implemented later with respect to the running direction of a board | substrate. did.

In the sputtering film formation, the distance between the target and the substrate is 75 mm, and when the degree of vacuum in the chamber reaches 2 × 10 ⁻⁴ to 1 × 10 ⁻⁴ Pa, Ar gas having a purity of 99.9999% is introduced into the chamber. The gas pressure was 0.3 to 8.0 Pa. In the case of dual magnetron sputtering, AC power was 1000 to 2000 W, and in the case of double magnetron sputtering, the target input DC power density was 0.7 to 5.2 W / cm ² to generate plasma. A film having a predetermined film thickness was formed on the substrate while the substrate was running without heating the substrate.

<Evaluation of membrane properties>
(A) Regular reflectance and parallel light transmittance of diamond-like carbon (DLC) gradient black coating film The regular reflectance of the obtained diamond-like carbon (DLC) gradient black coating film at wavelengths of 380 to 780 nm The parallel light transmittance was measured with a spectrophotometer (V-570 manufactured by JASCO Corporation), and the optical density (denoted as OD) was calculated from the parallel light transmittance (T) according to the following equation (2). .

The regular reflectance of light of the black coating film refers to the reflectance of light reflected from the surface at an angle equal to the incident angle of incident light according to the law of reflection. The incident angle was measured at 5 °. The parallel light transmittance means a parallel component of light rays that pass through the diamond-like carbon (DLC) gradient structure black coating film, and is expressed by the following equation.

(B) Composition of diamond-like carbon (DLC) gradient structure black coating film, surface irregularities Composition of the obtained diamond-like carbon (DLC) gradient structure black coating film (O / Ti atom ratio, C / Ti atom number) The ratio was calculated by calculating the Ti amount, O amount, and C amount in the depth direction of the film with a scanning X-ray photoelectron spectrometer (SAM-4300 manufactured by ULVAC-PHI).
Note that since the surface of the film is bonded with a large amount of oxygen, the composition of the film surface was measured after removing it by sputtering to a depth of about 10 nm in vacuum. Further, the composition in the depth direction was measured by repeating sputtering and measurement. The cross-sectional structure of the film was observed using a high-resolution transmission electron microscope (sometimes referred to as TEM). Further, the surface roughness of the black coating film was measured using an atomic force microscope (sometimes referred to as AFM).

(C) Evaluation of carbon bonding state of diamond-like carbon (DLC) gradient structure black coating film Diamond-like carbon (DLC) gradient structure black coating film obtained by using Micro Laser Raman (SENTERRA) manufactured by Bruker Optics The mixed state of sp2-bonded carbon and sp3-bonded carbon of the component of the carbon in the inside was investigated. From the Raman spectrum, the Raman peaks of sp2-bonded carbon and sp3-bonded carbon derived from carbon were evaluated by performing peak fitting with a Gaussian waveform.

The L ^* values obtained L ^* values of the light shielding plate (d) light shielding plate, colorimeter at (BYK-Gardner GmbH trade name spectrometer guide), a light source D65, was measured at a viewing angle of 10 ° .

(E) Dynamic friction coefficient About the dynamic friction coefficient of the obtained black light-shielding plate, it evaluated based on JISK7125 using the tensile tester (5566 type made from INSTRON).

(F) Wettability to water The wettability of the obtained black light shielding plate to water was evaluated by measuring the contact angle using a fully automatic contact angle measuring device (OCA35 manufactured by Data Physics Co., Ltd.). The measurement conditions were a Hamilton syringe 500 μL as the dropping syringe, a needle SNS021 / 011 as the dropping needle, a droplet supply speed of 1 μL / sec, a dropping amount of 3 μL, and room temperature.

(G) Ultraviolet resistance Using a conveyor type ultraviolet irradiation device, the light source was a high pressure mercury lamp, the ultraviolet irradiation intensity was 256 mW / cm ² , and the irradiation time was 40 minutes, and the presence or absence of deformation and discoloration was evaluated.

As a combination of targets, using a titanium target and a carbon sintered body target, only argon (Ar) gas is introduced on a glass substrate (Corning 7059) having a thickness of 1.1 mm, which is a substrate by dual magnetron sputtering, The alternating current power was maintained at 1000 W, and sputtering film formation was performed so that the film thickness became 200 nm with a film formation gas pressure of 1.5 Pa.
The duty ratio (ratio of sputtering time of each target) in the dual magnetron cathode was 0.5: 0.5 for each of the titanium target and the sintered carbon target.
The measurement results of the film properties are shown in Table 1.

The sputtering film formation was performed in the same manner as in Example 1 except that the film formation gas pressure was set to 3.0 Pa. The measurement results of the film properties are shown in Table 1.

The sputtering film formation was performed in the same manner as in Example 1 except that the film formation gas pressure was 6.0 Pa. The measurement results of the film properties are shown in Table 1.

The sputtering film formation was performed in the same manner as in Example 1 except that the AC power was maintained at 2000 W and the film formation gas pressure was 8.0 Pa. The measurement results of the film properties are shown in Table 1.

(Comparative Example 1)
Sputter deposition was performed in the same manner as in Example 1 except that the AC power was maintained at 2000 W and the deposition gas pressure was 1.4 Pa. The measurement results of the produced film characteristics are shown in Table 1.

In Examples 1 to 4, the film was formed by introducing only Ar gas at a film forming gas pressure of 1.5 to 8.0 Pa. As shown in Table 1, the composition in the film thickness direction was C / Ti atomic ratio. It was 2.05 to 29.00. On the other hand, the O / Ti atomic ratio was 0.80 to 2.20.
In each of Examples 1 to 4, the C / Ti atomic ratio and the O / Ti atomic ratio were low on the substrate side and high on the film surface side.

The average specular light reflectance at a wavelength of 380 to 780 nm was as low as 10.8 to 15.1%, and a black film having an average transmittance of 21.8 to 53.4% was obtained.

In addition, it was confirmed that the carbon bonding state in the film was a mixture of sp2 bonded carbon and sp3 bonded carbon.
The dynamic friction coefficient of the film surface was 0.10 or less.
The contact angle with respect to water was 96 to 115 ° and 90 ° or more for any film, indicating excellent water repellency.
The arithmetic average height Ra of the film surface was 0.92 to 3.01 nm, and irregularities were formed on the film surface.

Furthermore, there was no discoloration of the film after the UV resistance test. Such a film is very useful as a surface coating film for shutter blades because it is black and has a low average specular reflectance, a very small coefficient of dynamic friction, and excellent water repellency and UV resistance. .

On the other hand, in Comparative Example 1 in which sputtering film formation was performed under the conditions of AC power 2000 W and gas pressure 1.4 Pa, the C / Ti atomic ratio was 1.58 to 5.10 as compared with the films of Examples 1 to 4. The O / Ti atomic ratio was as low as 0.53 to 0.75, and the film color was brown. Further, the average regular reflectance at wavelengths of 380 to 780 nm was 19.4%, which was higher than those of Examples 1 to 4, and the average transmittance was 19.7%, which was smaller.

The surface roughness (Ra) of the film was 0.75 nm, which was smaller than Example 1 and flat. The contact angle with water was 85 °, which was small compared to Examples 1 to 4, and the coefficient of dynamic friction was as large as 0.14. The UV resistance was good with no discoloration as in Examples 1 to 4.

Except for using a titanium carbide target and a sintered carbon target as a target combination, the AC power value, the deposition gas pressure, the duty ratio at the dual magnetron cathode, and the film thickness were the same as in Example 1. A film was formed on top. The measurement results of the film properties are shown in Table 1.

Except for using a titanium carbide target and a sintered carbon target as a target combination, the AC power value, the deposition gas pressure, the duty ratio at the dual magnetron cathode, and the film thickness were the same as in Example 2, and the glass substrate A film was formed on top. The measurement results of the film properties are shown in Table 1.

As a combination of targets, except that a titanium carbide target and a carbon sintered body target were used, the film forming gas pressure, the duty ratio at the dual magnetron cathode, and the film thickness were the same as in Example 3, and the film was formed on the glass substrate. Formed. The measurement results of the film properties are shown in Table 1.

(Comparative Example 2)
Sputter deposition was performed in the same manner as in Example 5 except that the AC power was maintained at 2000 W and the deposition gas pressure was 1.4 Pa. The measurement results of the film properties are shown in Table 1.

(Comparative Example 3)
A sputtering film was formed in the same manner as in Example 5 except that the AC power was maintained at 1000 W and the film forming gas pressure was 8.0 Pa. The measurement results of the film properties are shown in Table 1.

In Examples 5 to 7, the C / Ti atom number ratio in the film was 2.05 to 30.00, and the O / Ti atom number ratio was 0.80 to 2.10. The Ti atom number ratio was low on the substrate side and high on the film surface side, and the O / Ti atom number ratio was low on the substrate side and high on the film surface side.
An average regular reflectance at a wavelength of 380 to 780 nm was as low as 10.6 to 16.9%, and a black film having an average transmittance of 22.4 to 34.6% was obtained.
The surface roughness (Ra) of the film was 3.42 to 4.11 nm, and irregularities were formed on the film surface.

In addition, the carbon bonding state in the film was confirmed to be a mixture of sp2-bonded carbon and sp3-bonded carbon.
The dynamic friction coefficient of the film surface was 0.10 or less, and the contact angle with water was 98 to 124 ° and 90 ° or more for all films, indicating that the film was excellent in water repellency. Furthermore, there was no discoloration of the film after the UV resistance test.
Such a film is very useful as a surface coating film for shutter blades because it is black and has a low average specular reflectance, a very small coefficient of dynamic friction, and excellent water repellency and UV resistance. .

In Comparative Example 2, the C / Ti atom number ratio in the film is 1.95 to 18.70, compared with the films of Examples 5 to 7 formed at a gas pressure of 1.5 Pa or more, and the O / Ti atom ratio. Was as low as 0.65 to 0.78, and the film color was brown. The average regular reflectance at wavelengths of 380 to 780 nm was as high as 18.6%, and the average transmittance was as low as 18.9%. The surface roughness (Ra) of the film was 0.78 nm, which was smaller than Example 1 and was flat. The contact angle with water was 88 °, which was smaller than those in Examples 5 to 7, and the dynamic friction coefficient was as large as 0.17. The UV resistance was good with no discoloration as in Examples 5-7.

On the other hand, in Comparative Example 3, as can be seen from Table 1, the C / Ti atomic number ratio in the film was 4.37 to 31.20, and the O / Ti atomic number ratio was 1.78 to 2.28. The film surface portion was higher than ˜7, the average regular reflectance was low, and the average transmittance was high.
In addition, although the film surface was uneven and the arithmetic average height Ra was large, the kinetic friction coefficient and water repellency were inferior because the convex portion had a rounded shape.
Accordingly, in Comparative Example 2, the average regular reflectance is high, the blackness is low, the contact angle with water is small, and the dynamic friction coefficient is high. In Comparative Example 3, the optical characteristics are good, but the contact angle is small. Since the coefficient of dynamic friction is also high, it was not suitable as a surface coating film for shutter blade materials.

The target type and film forming gas pressure were prepared in the same manner as in Example 3 except that the thickness of the diamond-like carbon (DLC) gradient structure black coating film was 20 nm. The measurement results of the film properties are shown in Table 1.
The C / Ti atomic ratio in the film is 2.96 to 24.3 and the O / Ti atomic ratio is 0.95 to 1.55. Both the C / Ti atomic ratio and the O / Ti atomic ratio are on the film surface. Got higher on the side.

A black film having an average regular reflectance of 17.8% and an average transmittance of 48.6% at a wavelength of 380 to 780 nm of the obtained diamond-like carbon (DLC) gradient structure black coating film wavelength was obtained. The surface roughness (Ra) of the film was 0.84 nm, and irregularities were formed on the film surface.

In addition, the carbon bonding state in the film was confirmed to be a mixture of sp2-bonded carbon and sp3-bonded carbon.
The dynamic friction coefficient of the film surface was 0.09, the contact angle with water was 91 °, and it was found that water repellency was excellent. Furthermore, there was no discoloration of the film after the UV resistance test.
Such a film is very useful as a surface coating film for shutter blades because it is black and has a low average specular reflectance, a very small coefficient of dynamic friction, and excellent water repellency and UV resistance. .

(Comparative Example 4)
The target type and deposition gas pressure were prepared in the same manner as in Example 3 except that the thickness of the diamond-like carbon (DLC) gradient structure black coating film was 17 nm. The measurement results of the film properties are shown in Table 1.
The C / Ti atomic ratio in the film was 3.04 to 21.5, the O / Ti atomic ratio was 0.62 to 0.79, and the O / Ti atomic ratio was lower than that in Example 3. .

The obtained diamond-like carbon (DLC) graded black coating film has an average regular reflectance of 21.4% and an average transmittance of 52.3% at a wavelength of 380 to 780 nm, which is higher than that of Example 3. became. The color of the obtained film was brown. The surface roughness (Ra) of the film was 0.78 nm, and irregularities were formed on the film surface.

The bonding state of carbon in the film was confirmed to be a mixture of sp2-bonded carbon and sp3-bonded carbon.
The dynamic friction coefficient of the film surface was 0.09, and the contact angle with water was 84 °. Furthermore, there was no discoloration of the film after the UV resistance test.
Therefore, the dynamic friction coefficient and ultraviolet resistance are the same as in Example 3, but the film of Comparative Example 4 having a small contact angle with water, a brown film color, and a high average regular reflectance and a high average transmittance is low in reflection and It is inappropriate as a surface coating film for shutter blades where black is desired.

The target type and film forming gas pressure were prepared in the same manner as in Example 7 except that the thickness of the diamond-like carbon (DLC) gradient structure black coating film was 20 nm. The measurement results of the film properties are shown in Table 1.
The C / Ti atomic ratio in the film is 2.38 to 29.4 and the O / Ti atomic ratio is 0.88 to 1.45. Both the C / Ti atomic ratio and the O / Ti atomic ratio are on the film surface. Got higher on the side.

A black film having an average regular reflectance of 16.2% and an average transmittance of 49.1% at a wavelength of 380 to 780 nm of the obtained diamond-like carbon (DLC) gradient structure black coating film wavelength was obtained. The surface roughness (Ra) of the film was 0.93 nm, and irregularities were formed on the film surface.

In addition, the carbon bonding state in the film was confirmed to be a mixture of sp2-bonded carbon and sp3-bonded carbon.
The dynamic friction coefficient of the film surface was 0.10, the contact angle with water was 93 °, and it was found that water repellency was excellent. Furthermore, there was no discoloration of the film after the UV resistance test.
Such a film is very useful as a surface coating film for shutter blades because it is black and has a low average specular reflectance, a very small coefficient of dynamic friction, and excellent water repellency and UV resistance. .

(Comparative Example 5)
The target type and film forming gas pressure were prepared in the same manner as in Example 7 except that the film thickness of the diamond-like carbon (DLC) gradient structure black coating film was 17 nm. The measurement results of the film properties are shown in Table 1.
The C / Ti atomic ratio in the film was 2.21 to 27.3, the O / Ti atomic ratio was 0.52 to 0.70, and the O / Ti atomic ratio was lower than that in Example 7. .

The obtained diamond-like carbon (DLC) gradient structure black coating film had an average regular reflectance of 20.7% and an average transmittance of 50.4% at a wavelength of 380 to 780 nm, both of which were higher than those of Example 7. became. The color of the obtained film was brown. The surface roughness (Ra) of the film was 0.74 nm, and irregularities were formed on the film surface.

The bonding state of carbon in the film was confirmed to be a mixture of sp2-bonded carbon and sp3-bonded carbon.
The dynamic friction coefficient of the film surface was 0.09, and the contact angle with water was 87 °. Furthermore, there was no discoloration of the film after the UV resistance test.
Therefore, the dynamic friction coefficient, water repellency, and UV resistance are the same as in Example 7, but the film of Comparative Example 5 having a brown film color and high average regular reflectance and high average transmittance is low reflective and black. It is unsuitable as a surface coating film for a shutter blade material for which water repellency is desired.

A titanium target and a sintered carbon target were used as the sputtering target, and the cathode system used for film formation was changed to a double magnetron cathode.
Film formation was performed with an input power density of the titanium target of 5.2 W / cm ² and an input power density of the carbon sintered body target of 1.3 W / cm ² .
The film thickness was about 200 nm, the film forming gas pressure was 1.5 Pa, and a diamond-like carbon (DLC) gradient structure black coating film was formed on a glass substrate. The measurement results of the film properties are shown in Table 2.

The C / Ti atomic ratio in the film was 2.32 to 7.50, which was higher on the film surface side. Further, the O / Ti atomic ratio was 0.85 to 0.96, and the O / Ti atomic ratio was higher on the film surface side.

The average regular reflectance at a wavelength of 380 to 780 nm of the obtained diamond-like carbon (DLC) gradient structure black coating film was 17.6%. A black film having an average transmittance of 35.0% was obtained. The surface roughness (Ra) of the film was 0.99 nm, and irregularities were formed on the film surface.

The bonding state of carbon in the film was confirmed to be a mixture of sp2-bonded carbon and sp3-bonded carbon.
The dynamic friction coefficient of the film surface was 0.10. The contact angle with water was 93 °, and it was found that the water repellency was excellent. Furthermore, there was no discoloration of the film after the UV resistance test.
The film of Example 10, which is black and has a low average regular reflectance, a very small dynamic friction coefficient, and excellent water repellency and UV resistance, is very useful as a surface coating film for shutter blade materials.

A diamond-like carbon (DLC) gradient structure black coating film was produced on a glass substrate under the same conditions as in Example 10 except that the film forming gas pressure was 6.0 Pa. The measurement results of the film properties are shown in Table 2.
The C / Ti atom number ratio in the film was 2.69 to 21.53, which was higher on the film surface side. Further, the O / Ti atomic ratio was 1.25 to 1.94, and the O / Ti atomic ratio was higher on the film surface side.

The obtained diamond-like carbon (DLC) gradient structure black coating film had a wavelength of 380 to 780 nm with an average regular reflectance of 14.2%, and a black film with an average transmittance of 47.1% was obtained. .
The surface roughness (Ra) of the film was 2.77 nm, and irregularities were formed on the film surface.

The bonding state of carbon in the film was confirmed to be a mixture of sp2-bonded carbon and sp3-bonded carbon.
The dynamic friction coefficient of the film surface was 0.10, the contact angle with water was 108 °, and it was found that water repellency was excellent. Furthermore, there was no discoloration of the film after the UV resistance test.
Such a film of Example 11 which is black and has a low average specular reflectance, a very small dynamic friction coefficient, and excellent water repellency and UV resistance is very useful as a surface coating film of a shutter blade material.

A diamond-like carbon (DLC) gradient structure black coating film was produced on a glass substrate in the same manner as in Example 10 except that the gas pressure was changed to 8.0 Pa. The measurement results of the film properties are shown in Table 2.
The C / Ti atomic ratio in the film was 4.28 to 28.70, which was higher on the film surface side. Further, the O / Ti atomic ratio was 1.64 to 2.20, and the O / Ti atomic ratio was higher on the film surface side.

The resulting diamond-like carbon (DLC) gradient structure black coating film obtained a black film having an average regular reflectance of 12.7% and an average transmittance of 50.3% at a wavelength of 380 to 780 nm. The surface roughness (Ra) of the film was 3.17 nm, and uneven projections were formed on the film surface.

The bonding state of carbon in the film was confirmed to be a mixture of sp2-bonded carbon and sp3-bonded carbon.
The dynamic friction coefficient of the film surface was 0.08, the contact angle with water was 120 °, and it was found that water repellency was excellent. Furthermore, there was no discoloration of the film after the UV resistance test.
Such a film of Example 12, which is black and has a low average specular reflectance, a very small dynamic friction coefficient, and excellent water repellency and UV resistance, is very useful as a surface coating film for shutter blade materials.

(Comparative Example 6)
A diamond-like carbon (DLC) gradient structure black coating film was produced in the same manner as in Example 10 except that the film forming gas pressure was changed to 0.3 Pa, in the same manner as in Example 10. The measurement results of the film properties are shown in Table 2.
The C / Ti atomic ratio in the film was 0.95 to 10.52, which was higher on the film surface side. Further, the O / Ti atom number ratio was 0.45 to 0.62, which was higher on the film surface side as in the C / Ti atom number ratio. The O / Ti atomic ratio was smaller than that in Example 10.

The average regular reflectance at a wavelength of 380 to 780 nm of the obtained diamond-like carbon (DLC) gradient structure black coating film was 24.5%, and the average transmittance was 4.5%.
Compared to Example 10, the average regular reflectance was high and the average transmittance was low. The film color was yellow or brown and was not black. The surface roughness (Ra) of the film was 0.74 nm, which was smaller than that of Example 10, and the film surface was flat.

The bonding state of carbon in the film was confirmed to be a mixture of sp2-bonded carbon and sp3-bonded carbon.
The dynamic friction coefficient of the film surface was 0.28, which was larger than that of Example 10. The contact angle with water was less than 90 °, indicating that the water repellency was poor. There was no discoloration of the film after the UV resistance test.
Such a film color is not black, the average regular reflectance is high, the average transmittance is low, the dynamic friction coefficient is large, and the water repellency is poor. The film of Comparative Example 6 is low reflection and black and has low dynamic friction. It is inappropriate as a surface coating film for a shutter blade material for which a coefficient is desired.

(Comparative Example 7)
A diamond-like carbon (DLC) gradient structure black coating film was produced in the same manner as in Example 10 except that the film forming gas pressure was changed to 1.4 Pa. The measurement results of the film properties are shown in Table 2.

The C / Ti atomic ratio in the film was 1.48 to 15.88, which was higher on the film surface side. Further, the O / Ti atom number ratio was 0.67 to 0.78, which was higher on the film surface side as in the C / Ti atom number ratio. The O / Ti atomic ratio was smaller than that in Example 10.

The average regular reflectance at a wavelength of 380 to 780 nm of the obtained diamond-like carbon (DLC) gradient structure black coating film was 18.9%, and the average transmittance was 15.7%. The average regular reflectance was high and the average transmittance was low.
The film color was yellow or brown and was not black.
The surface roughness (Ra) of the film was 0.45 nm, which was smaller than that of Example 10, and the film surface was flat.

The bonding state of carbon in the film was confirmed to be a mixture of sp2-bonded carbon and sp3-bonded carbon.
The dynamic friction coefficient of the film surface was 0.13, which was larger than that of Example 10. The contact angle with water was less than 90 °, indicating that the water repellency was poor. There was no discoloration of the film after the UV resistance test.
Such a film color is not black, the average regular reflectance is high, the average transmittance is low, the dynamic friction coefficient is large, and the water repellency is poor. The film of Comparative Example 7 is low in reflection and black and has low dynamic friction. It is inappropriate as a surface coating film for a shutter blade material for which a coefficient is desired.

(Comparative Example 8)
A diamond-like carbon (DLC) gradient structure black coating film was produced on a glass substrate in the same manner as in Example 12 except that the input power density of the target 2 was changed to 0.7 W / cm ² . The measurement results of the film properties are shown in Table 2.
The C / Ti atomic ratio in the film was 4.50 to 29.90, which was higher on the film surface side. The O / Ti atomic ratio was 1.84 to 2.38, and the O / Ti atomic ratio was higher on the film surface side.

The resulting diamond-like carbon (DLC) gradient structure black coating film had a black film having an average regular reflectance of 10.2% and an average transmittance of 52.7% at a wavelength of 380 to 780 nm. The surface roughness (Ra) of the film was 3.87 nm, and irregularities were formed on the film surface. However, the tip of the convex portion was rounder than that of Example 12.

In addition, the carbon bonding state in the film was confirmed to be a mixture of sp2-bonded carbon and sp3-bonded carbon.
The dynamic friction coefficient of the film surface was 0.17, and the contact angle with water was 88 °, which was inferior to that of Example 12. Furthermore, there was no discoloration of the film after the UV resistance test.
Since Comparative Example 8 having such a large coefficient of dynamic friction and poor water repellency becomes unstable in operation at high temperature and high humidity, it cannot be used as a surface coating film for shutter blade materials.

Film formation was performed in the same manner as in Example 10 except that the titanium carbide target and the carbon sintered body target were used as the sputtering target, and the film formation gas pressure, target input power density, and film thickness were the same. The measurement results of the film properties are shown in Table 2.
The C / Ti atomic ratio in the film was 2.25 to 20.30, which was higher on the film surface side. Further, the O / Ti atomic ratio was 0.82 to 0.94, which was higher on the film surface side.

The obtained diamond-like carbon (DLC) gradient structure black coating film had a black film having an average regular reflectance of 15.6% and an average transmittance of 24.6% at a wavelength of 380 to 780 nm. The surface roughness (Ra) of the film was 1.24 nm, and irregularities were formed on the film surface.

The bonding state of carbon in the film was confirmed to be a mixture of sp2-bonded carbon and sp3-bonded carbon.
The dynamic friction coefficient of the film surface was 0.10, the contact angle with water was 103 °, and it was found that water repellency was excellent. Furthermore, there was no discoloration of the film after the UV resistance test.
The film of Example 13, which is black and has a low average regular reflectance, a very small dynamic friction coefficient, and excellent water repellency and UV resistance, is very useful as a surface coating film for shutter blade materials.

Except that the film forming gas pressure was changed to 6.0 Pa, the target type, target input power density, and film thickness were formed in the same manner as in Example 13. The measurement results of the film properties are shown in Table 2.
The C / Ti atomic ratio in the film was 2.75 to 28.60, which was higher on the film surface side. Further, the O / Ti atomic ratio was 1.15 to 2.05, which was higher on the film surface side.

The resulting diamond-like carbon (DLC) gradient structure black coating film obtained a black film having an average regular reflectance of 11.5% and an average transmittance of 38.6% at a wavelength of 380 to 780 nm. The surface roughness (Ra) of the film was 2.66 nm, and irregularities were formed on the film surface.

The bonding state of carbon in the film was confirmed to be a mixture of sp2-bonded carbon and sp3-bonded carbon.
The dynamic friction coefficient of the film surface was 0.08, the contact angle with water was 119 °, and it was found that water repellency was excellent. Furthermore, there was no discoloration of the film after the UV resistance test.
Such a film of Example 14 which is black and has a low average specular reflectance, a very small dynamic friction coefficient, and excellent water repellency and UV resistance is very useful as a surface coating film for a shutter blade material.

(Comparative Example 9)
A diamond-like carbon (DLC) gradient structure black coating film was produced in the same manner as in Example 13 except that the film forming gas pressure was changed to 0.3 Pa, in the same manner as in Example 13. The measurement results of the film properties are shown in Table 2.
The C / Ti atomic ratio in the film was 1.36 to 9.20, which was higher on the film surface side. Further, the O / Ti atomic ratio was 0.35 to 0.52, which was higher on the film surface side as in the C / Ti atomic ratio. Compared to Example 13, the O / Ti atomic ratio was small.

The average regular reflectance at a wavelength of 380 to 780 nm of the obtained diamond-like carbon (DLC) gradient structure black coating film was 21.6%, and the average transmittance was 8.7%. Compared to Example 13, the average regular reflectance was high and the average transmittance was low. The film color was yellow or brown and was not black. The surface roughness (Ra) of the film was 0.66 nm, which was smaller than that of Example 13, and the film surface was flat.

The bonding state of carbon in the film was confirmed to be a mixture of sp2-bonded carbon and sp3-bonded carbon.
The dynamic friction coefficient of the film surface was 0.21, which was larger than that of Example 13. The contact angle with water was less than 90 °, indicating that the water repellency was poor. There was no discoloration of the film after the UV resistance test.
Such a film color is not black, the average regular reflectance is high, the average transmittance is low, the dynamic friction coefficient is large, and the film of Comparative Example 9 having poor water repellency is low reflection and black and has a low dynamic friction coefficient. Is inappropriate as a surface coating film for a desired shutter blade material.

(Comparative Example 10)
A diamond-like carbon (DLC) gradient structure black coating film was produced in the same manner as in Example 13 except that the film forming gas pressure was changed to 1.4 Pa. The measurement results of the film properties are shown in Table 2.
The C / Ti atom number ratio in the film was 1.88 to 27.62, which was higher on the film surface side. Further, the O / Ti atomic ratio was 0.54 to 0.76, which was higher on the film surface side as in the C / Ti atomic ratio. Compared to Example 13, the O / Ti atomic ratio was small.

The average regular reflectance at a wavelength of 380 to 780 nm of the obtained diamond-like carbon (DLC) gradient structure black coating film was 19.4%, and the average transmittance was 18.3%. Compared to Example 13, the average regular reflectance was high and the average transmittance was low. The film color was yellow or brown and was not black. The surface roughness (Ra) of the film was 0.76 nm, which was smaller than that of Example 13, and the film surface was flat.

The bonding state of carbon in the film was confirmed to be a mixture of sp2-bonded carbon and sp3-bonded carbon.
The dynamic friction coefficient on the film surface was 0.15, which was larger than that in Example 13. The contact angle with water was less than 90 °, indicating that the water repellency was poor. There was no discoloration of the film after the UV resistance test.
Such a film color is not black, the average regular reflectance is high, the average transmittance is low, the dynamic friction coefficient is large, and the water repellency is poor. The film of Comparative Example 10 is low reflective and black and has a low dynamic friction coefficient. Is inappropriate as a surface coating film for a desired shutter blade material.

Except for changing the film thickness of the diamond-like carbon (DLC) gradient structure black coating film to 20 nm, the film was formed in the same manner as in Example 11 except that the input power density, film formation gas pressure, and target type of the target were the same. . The measurement results of the film properties are shown in Table 2.
The C / Ti atomic ratio in the film was 2.96 to 24.30, which was higher on the film surface side. Further, the O / Ti atomic ratio was 0.95 to 1.55, which was higher on the film surface side.

The resulting diamond-like carbon (DLC) gradient structure black coating film obtained a black film having an average regular reflectance of 17.8% and an average transmittance of 48.6% at a wavelength of 380 to 780 nm. The surface roughness (Ra) of the film was 0.84 nm, and irregularities were formed on the film surface.

The bonding state of carbon in the film was confirmed to be a mixture of sp2-bonded carbon and sp3-bonded carbon.
The dynamic friction coefficient of the film surface was 0.09, the contact angle with water was 91 °, and it was found that water repellency was excellent. Furthermore, there was no discoloration of the film after the UV resistance test.
The film of Example 15 which is black and has a low average regular reflectance, a very small dynamic friction coefficient, and excellent water repellency and UV resistance is very useful as a surface coating film for a shutter blade material.

Except that the film thickness of the diamond-like carbon (DLC) gradient structure black coating film was changed to 20 nm, the film was formed in the same manner as in Example 14 except that the input power density, film formation gas pressure, and target type of the target were the same. .
The C / Ti atomic ratio in the film was 2.38 to 29.4, which was higher on the film surface side. Further, the O / Ti atom number ratio was 0.88 to 1.45, which was higher on the film surface side.

The resulting diamond-like carbon (DLC) gradient structure black coating film obtained a black film having an average regular reflectance of 16.2% and an average transmittance of 49.1% at a wavelength of 380 to 780 nm. The surface roughness (Ra) of the film was 0.93 nm, and irregularities were formed on the film surface.

The bonding state of carbon in the film was confirmed to be a mixture of sp2-bonded carbon and sp3-bonded carbon.
The dynamic friction coefficient of the film surface was 0.10, the contact angle with water was 93 °, and it was found that water repellency was excellent. Furthermore, there was no discoloration of the film after the UV resistance test.
The film of Example 16, which is black and has a low average regular reflectance, a very small dynamic friction coefficient, and excellent water repellency and UV resistance, is very useful as a surface coating film for a shutter blade material.

Film formation was performed in the same manner as in Example 10 except that the input power density of the target 1 was changed to 3.9 W / cm ² , and the film formation gas pressure, the target type, and the film thickness. The measurement results of the film properties are shown in Table 2.
The C / Ti atomic ratio in the film was 2.79 to 22.53, which was higher on the film surface side. Further, the O / Ti atomic ratio was 1.15 to 2.06, which was higher on the film surface side.

The resulting diamond-like carbon (DLC) gradient structure black coating film had a black film having an average regular reflectance of 15.3% and an average transmittance of 30.0% at a wavelength of 380 to 780 nm. The surface roughness (Ra) of the film was 1.15 nm, and irregularities were formed on the film surface.

The bonding state of carbon in the film was confirmed to be a mixture of sp2-bonded carbon and sp3-bonded carbon.
The dynamic friction coefficient of the film surface was 0.10, the contact angle with water was 93 °, and it was found that water repellency was excellent. Furthermore, there was no discoloration of the film after the UV resistance test.
Such a film of Example 17 which is black and has a low average specular reflectance, a very small dynamic friction coefficient, and excellent water repellency and UV resistance is very useful as a surface coating film of a shutter blade material.

Film formation was performed in the same manner as in Example 13 except that the input power density of the target was changed to 3.9 W / cm ² , and the film formation gas pressure, the target type, and the film thickness. The measurement results of the film properties are shown in Table 2.
The C / Ti atom number ratio in the film was 2.68 to 21.53, which was higher on the film surface side. Further, the O / Ti atomic number ratio was 1.35 to 2.10, which was higher on the film surface side.

The resulting diamond-like carbon (DLC) gradient structure black coating film obtained a black film having an average regular reflectance of 14.1% and an average transmittance of 40.5% at a wavelength of 380 to 780 nm. The surface roughness (Ra) of the film was 1.27 nm, and irregularities were formed on the film surface.

The bonding state of carbon in the film was confirmed to be a mixture of sp2-bonded carbon and sp3-bonded carbon.
The dynamic friction coefficient of the film surface was 0.10. The contact angle with water was 95 °, and it was found that the water repellency was excellent. Furthermore, there was no discoloration of the film after the UV resistance test.
Such a film of Example 18 which is black and has a low average regular reflectance, a very small dynamic friction coefficient, and excellent water repellency and UV resistance is very useful as a surface coating film of a shutter blade material.

(Comparative Example 11)
Film formation was performed in the same manner as in Example 10 except that the film thickness of the diamond-like carbon (DLC) gradient structure black coating film was changed to 17 nm, and the film formation gas pressure, target type, and target input power density were the same. . The measurement results of the film properties are shown in Table 2.
The C / Ti atomic ratio in the film was 3.27 to 21.5, and the O / Ti atomic ratio was 0.43 to 0.69. Similarly, the C / Ti atom number ratio and the O / Ti atom number ratio increased on the film surface side. Compared to Example 10, the O / Ti atomic ratio was small.

The resulting diamond-like carbon (DLC) gradient structure black coating film had an average regular reflectance of 22.5% at a wavelength of 380 to 780 nm and an average transmittance of 48.2%. Compared to Example 10, the average regular reflectance was high. Moreover, the film color was brown and not black. The surface roughness (Ra) of the film was 0.62 nm, which was smaller than that of Example 10, and the film surface was flat.

The bonding state of carbon in the film was confirmed to be a mixture of sp2-bonded carbon and sp3-bonded carbon.
The dynamic friction coefficient of the film surface was 0.10, the contact angle with water was 81 °, and it was found that the water repellency was poor. There was no discoloration of the film after the UV resistance test.
Such a film color is not black, the average regular reflectance is high, and the film of Comparative Example 11 having poor water repellency is not suitable as a surface coating film of a shutter blade material that is desired to be low reflection and black. is there.

(Comparative Example 12)
Film formation was performed in the same manner as in Example 13 except that the film thickness of the diamond-like carbon (DLC) gradient structure black coating film was changed to 17 nm, and the film formation gas pressure, target type, and target input power density were the same. . The measurement results of the film properties are shown in Table 2.
The C / Ti atomic ratio in the film was 2.91 to 23.40, and the O / Ti atomic ratio was 0.50 to 0.73. Similarly, the C / Ti atom number ratio and the O / Ti atom number ratio increased on the film surface side. Compared to Example 13, the O / Ti atomic ratio was small.

The average regular reflectance at a wavelength of 380 to 780 nm of the obtained diamond-like carbon (DLC) gradient structure black coating film was 21.4%, and the average transmittance was 51.7%. Compared to Example 13, the average regular reflectance was high. Moreover, the film color was brown and not black. The surface roughness (Ra) of the film was 0.71 nm, which was smaller than that of Example 13, and the film surface was flat.

The bonding state of carbon in the film was confirmed to be a mixture of sp2-bonded carbon and sp3-bonded carbon.
The dynamic friction coefficient of the film surface was 0.10, and the contact angle with water was 80 °. There was no discoloration of the film after the UV resistance test.
Such a film color is not black, the average regular reflectance is high, and the film of Comparative Example 12 having poor water repellency is not suitable as a surface coating film of a shutter blade material that is desired to be low reflection and black. is there.

The substrate type is replaced with a SUS substrate having a thickness of 50 μm and a surface roughness (arithmetic average height Ra) of 0.25 μm, and diamond-like carbon (DLC) gradient structure black coating film is formed on the surface of both surfaces of the substrate. The film of Example 1 was formed to a thickness of 20 nm. Table 3 shows the measurement results of the film characteristics.

When the film shown in Example 19 was formed, the surface thereof was black and exhibited low reflection characteristics. Further, both of the contact angles with water showed high water repellency, the coefficient of dynamic friction was 0.10 or less, and there was no deformation or discoloration due to ultraviolet irradiation, and an optical member having excellent water repellency and dynamic coefficient of friction could be obtained.

Instead of a SUS substrate having a thickness of 50 μm and a surface roughness (arithmetic average height Ra) of 0.25 μm, the surface of the substrate is a diamond-like carbon (DLC) gradient structure black coating film on both surfaces of the substrate. The film of Example 5 was formed to a thickness of 100 nm. Table 3 shows the measurement results of the film characteristics.

When the film shown in Example 20 was formed, the surface thereof was black and exhibited low reflection characteristics. Further, both of the contact angles with water showed high water repellency, the coefficient of dynamic friction was 0.10 or less, and there was no deformation or discoloration due to ultraviolet irradiation, and an optical member having excellent water repellency and dynamic coefficient of friction could be obtained.

The film according to Example 1 was formed to a thickness of 20 nm in the same manner as in Example 19 except that the type of the substrate was changed to a Ti substrate having a thickness of 50 μm and a surface roughness (arithmetic average height Ra) of 0.23 μm. Produced. The film property evaluation is shown in Table 3.

As in Example 19, the film surface was black and exhibited low reflection characteristics. In addition, the contact angle with water showed high water repellency, the coefficient of dynamic friction was 0.10 or less, and there was no deformation or discoloration due to ultraviolet irradiation, and the optical member was excellent in water repellency and dynamic coefficient of friction. .

The film of Example 5 was formed to a thickness of 100 nm in the same manner as in Example 20, except that the type of substrate was changed to a Ti substrate having a thickness of 50 μm and a surface roughness (arithmetic average height Ra) of 0.23 μm. Produced. The film property evaluation is shown in Table 3.

As in Example 20, the film surface was black and exhibited low reflection characteristics. In addition, the contact angle with water showed high water repellency, the coefficient of dynamic friction was 0.10 or less, and there was no deformation or discoloration due to ultraviolet irradiation, and the optical member was excellent in water repellency and dynamic coefficient of friction. .

The film of Example 1 was formed to a thickness of 20 nm in the same manner as in Example 19 except that the type of substrate was changed to an Al substrate having a thickness of 50 μm and a surface roughness (arithmetic average height Ra) of 0.26 μm. Produced. The evaluation results of the film properties are shown in Table 3.

As in Example 19, the surface was black and exhibited low reflection characteristics. Further, both of the contact angles with water showed high water repellency, the coefficient of dynamic friction was 0.10 or less, and there was no deformation or discoloration due to ultraviolet irradiation, and an optical member having excellent water repellency and dynamic coefficient of friction could be obtained.

The film of Example 5 was formed to a thickness of 100 nm in the same manner as Example 20, except that the type of substrate was changed to an Al substrate having a thickness of 50 μm and a surface roughness (arithmetic average height Ra) of 0.26 μm. Produced. The evaluation results of the film properties are shown in Table 3.

As in Example 20, the surface was black and exhibited low reflection characteristics. Further, both of the contact angles with water showed high water repellency, the coefficient of dynamic friction was 0.10 or less, and there was no deformation or discoloration due to ultraviolet irradiation, and an optical member having excellent water repellency and dynamic coefficient of friction could be obtained.

The type of the substrate was changed to a polyimide film having a thickness of 38 μm and a surface roughness (arithmetic average height Ra) of 0.50 μm, and the film of Example 5 was formed to a thickness of 20 nm on the surface. Table 3 shows the measurement results of the film characteristics.

The type of the substrate was changed to a polyimide film having a thickness of 50 μm and a surface roughness (arithmetic average height Ra) of 0.50 μm, and the film of Example 5 was formed to a thickness of 20 nm on the surface. The evaluation results of the film properties are shown in Table 3.

The type of the substrate was changed to a polyimide film having a thickness of 75 μm and a surface roughness (arithmetic average height Ra) of 0.50 μm, and the film of Example 5 was formed to a thickness of 200 nm on the surface. Table 3 shows the measurement results of the film characteristics.

The films of Examples 25 to 27 were both black in surface and exhibited low reflection characteristics. Further, both of the contact angles with water showed high water repellency, the coefficient of dynamic friction was 0.10 or less, and there was no deformation or discoloration due to ultraviolet irradiation, and an optical member having excellent water repellency and dynamic coefficient of friction could be obtained.

The substrate was replaced with a PET film having a thickness of 38 μm and a surface roughness (arithmetic average height Ra) of 0.60 μm, and the film of Example 5 was formed on the surface thereof to a thickness of 20 nm. Table 3 shows the measurement results of the film characteristics.

The substrate was replaced with a PET film having a thickness of 50 μm and a surface roughness (arithmetic average height Ra) of 0.60 μm, and the film of Example 5 was formed on the surface thereof to a thickness of 20 nm. Table 3 shows the measurement results of the film characteristics.

The substrate was replaced with a PET film having a thickness of 75 μm and a surface roughness (arithmetic average height Ra) of 0.60 μm, and the film of Example 5 was formed on the surface thereof to a thickness of 200 nm. Table 3 shows the measurement results of the film characteristics.

The films of Examples 28 to 30 both had a black surface and exhibited low reflection characteristics. Further, both of the contact angles with water showed high water repellency, the coefficient of dynamic friction was 0.10 or less, and there was no deformation or discoloration due to ultraviolet irradiation, and an optical member having excellent water repellency and dynamic coefficient of friction could be obtained.

A titanium carbide film (film thickness: 100 nm) was formed as a first-layer metal light-shielding film on the surface of a polyimide film having an arithmetic average height (Ra) of 0.25 μm and a thickness of 38 μm. Then, as a second layer film on the surface of the metal light shielding film, the film of Example 1 was formed by 100 nm to produce a black light shielding plate.
In both cases, the first film having the same film thickness and the second film having the same film thickness are formed symmetrically on both surfaces of the polyimide film, so that the film-like black shading plate without warping is formed. Was made. The measurement results of the characteristics are shown in Table 4.

A titanium carbide film (film thickness: 100 nm) was formed as a first metal light-shielding film on the surface of a polyimide film having an arithmetic average height (Ra) of 0.25 μm and a thickness of 38 μm. Then, as a second layer film on the surface of the metal light shielding film, the film of Example 2 was formed by 103 nm to produce a black light shielding plate. In both cases, the first film having the same film thickness and the second film having the same film thickness are formed symmetrically on both surfaces of the polyimide film, so that the film-like black shading plate without warping is formed. Was made. The measurement results of the characteristics are shown in Table 4.

A titanium carbide film (thickness: 100 nm) was formed as a first-layer metal light-shielding film on the surface of a polyimide film having an arithmetic average height (Ra) of 0.25 μm and a thickness of 38 μm. Then, as the second layer film on the surface of the metal light-shielding film, the film of Example 3 was formed to a thickness of 105 nm to produce a black light-shielding plate. In both cases, the first film having the same film thickness and the second film having the same film thickness are formed symmetrically on both surfaces of the polyimide film, so that the film-like black shading plate without warping is formed. Was made. The measurement results of the characteristics are shown in Table 4.

(Comparative Example 13)
A titanium carbide film (thickness: 100 nm) is formed as a first-layer metal light-shielding film on the surface of a polyimide film having an arithmetic average height (Ra) of 0.25 μm and a thickness of 38 μm. As the second layer film, the film of Comparative Example 1 was formed by 110 nm. The measurement results of the characteristics are shown in Table 4.

The produced black light shielding plates of Examples 31 to 33 all had an average optical density greater than 4.0 at wavelengths of 380 to 780 nm, and exhibited complete light shielding properties.
The average regular reflectance was 0.46 to 0.65%.
The arithmetic average height (Ra) of the film surface was 0.20 μm, and the water contact angle was 96 to 105 °, indicating excellent water repellency.
The dynamic friction coefficient was 0.10 or less, and there was no deformation or discoloration of the film due to UV resistance. The lightness (L ^* value) of the black light shielding plate was 36 to 40, indicating that the blackness was high.
Therefore, the black light-shielding plates of Examples 31 to 33 are very useful as shutter blade materials because they are excellent in light-shielding properties, low reflectivity, water repellency, slipperiness, and ultraviolet resistance.

On the other hand, the black light shielding plate of Comparative Example 13 had an average optical density greater than 4.0 and complete light shielding properties as in Examples 31 to 33, and the arithmetic average height Ra of the film surface was 0.20 μm. The average regular reflectance was 2.80%, which was higher than those of Examples 31 to 33. The lightness (L ^* value) of the black light shielding plate was as high as 56, and the blackness was low. Moreover, the contact angle with respect to water was 88 degrees and less than 90 degrees, and the dynamic friction coefficient was 0.19.
Therefore, the black light-shielding plate of Comparative Example 13 is not suitable as a shutter blade material because it has poor average regular reflectance, lightness (L ^* value), water repellency, and slipperiness.
Table 4 shows the type of substrate, film configuration, and evaluation results.

A titanium carbide film having a thickness of 100 nm was formed as a first-layer metal light-shielding film on the surface of a polyimide film having an arithmetic average height (Ra) of 0.32 μm and a thickness of 25 μm. Next, as a second layer film on the surface of the metal light shielding film, the film of Example 1 was formed to a thickness of 105 nm to produce a black light shielding plate. In both cases, the first film having the same film thickness and the second film having the same film thickness are formed symmetrically on both surfaces of the polyimide film, so that the film-like black shading plate without warping is formed. Was made. The measurement results of the characteristics are shown in Table 4.

A titanium carbide film having a thickness of 100 nm was formed as a first-layer metal light-shielding film on the surface of a polyimide film having an arithmetic average height (Ra) of 0.32 μm and a thickness of 25 μm. Then, as the second layer film on the surface of the metal light-shielding film, the film of Example 3 was formed to a thickness of 105 nm to produce a black light-shielding plate. In both cases, the first film having the same film thickness and the second film having the same film thickness are formed symmetrically on both surfaces of the polyimide film, so that the film-like black shading plate without warping is formed. Was made. The measurement results of the characteristics are shown in Table 4.

(Comparative Example 14)
In Comparative Example 14, an arithmetic average height (Ra) is 0.32 μm, and a titanium carbide film (film thickness: 100 nm) is formed as a first-layer metal light-shielding film on the surface of a polyimide film having a thickness of 25 μm. A film of Comparative Example 1 having a thickness of 105 nm was formed as a second film on the surface of the metal light-shielding film. The measurement results of the characteristics are shown in Table 4.

The produced black light-shielding plates of Examples 34 and 35 both had an average optical density greater than 4.0 at wavelengths of 380 to 780 nm and exhibited complete light-shielding properties.
Further, the average regular reflectance was 0.52 to 0.77%, which was 0.8% or less. The arithmetic average height (Ra) of the film surface was 0.22 μm, and the water contact angle was 105 to 118 °, indicating excellent water repellency. The dynamic friction coefficient was 0.10.
There was no film deformation or discoloration due to UV resistance. The lightness (L ^* value) of the black light shielding plate was 38 to 40, indicating that the blackness was high.
Therefore, the black light-shielding plates of Examples 34 and 35 are extremely useful as shutter blade materials because they are excellent in light-shielding properties, low reflectivity, water repellency, slipperiness, and ultraviolet resistance.

On the other hand, the black light-shielding plate of Comparative Example 14 had an average optical density greater than 4.0 as in Examples 34 and 35, had a complete light-shielding property, and the arithmetic average height Ra of the film surface was 0.22 μm. However, the average regular reflectance was 2.03%, which was higher than those in Examples 34 and 35. The lightness (L ^* value) of the black light shielding plate was as high as 49, and the blackness was low. Moreover, the contact angle with respect to water was 76 ° and less than 90 °, and the dynamic friction coefficient was 0.20.
Therefore, the black light-shielding plate of Comparative Example 14 is not suitable as a shutter blade material because it has poor average regular reflectance, lightness (L ^* value), water repellency, and slipperiness. Table 4 shows the type of substrate, film configuration, and evaluation results.

A titanium carbide film having a thickness of 100 nm was formed as a first-layer metal light-shielding film on the surface of a polyimide film having an arithmetic average height (Ra) of 0.43 μm and a thickness of 38 μm. Next, a film of Example 1 having a thickness of 105 nm was formed as a second film on the surface of the metal light-shielding film to produce a black light-shielding plate. In both cases, the first film having the same film thickness and the second film having the same film thickness are formed symmetrically on both surfaces of the polyimide film, so that the film-like black shading plate without warping is formed. Was made. The measurement results of the characteristics are shown in Table 4.

A titanium carbide film having a thickness of 100 nm was formed as a first-layer metal light-shielding film on the surface of a polyimide film having an arithmetic average height (Ra) of 0.43 μm and a thickness of 38 μm. Next, a film of Example 3 having a thickness of 105 nm was formed as a second film on the surface of the metal light-shielding film to produce a black light-shielding plate. In both cases, the first film having the same film thickness and the second film having the same film thickness are formed symmetrically on both surfaces of the polyimide film, so that the film-like black shading plate without warping is formed. Was made. The measurement results of the characteristics are shown in Table 4.

(Comparative Example 15)
In Comparative Example 15, an arithmetic average height (Ra) is 0.43 μm, and a titanium carbide film (film thickness: 100 nm) is formed as a first-layer metal light-shielding film on the surface of the polyimide film having a thickness of 38 μm. A film of Comparative Example 1 having a thickness of 105 nm was formed as a second layer film on the surface of the metal light-shielding film. The measurement results of the characteristics are shown in Table 4.

The produced black light-shielding plates of Examples 36 and 37 both had an average optical density greater than 4.0 at wavelengths of 380 to 780 nm and exhibited complete light-shielding properties. The average regular reflectance was 0.47 to 0.72%, which was 0.8% or less. The arithmetic average height (Ra) of the film surface was 0.35 μm, and the contact angle with water was 105 to 120 °, indicating excellent water repellency. The dynamic friction coefficient was 0.10, and there was no deformation or discoloration of the film due to UV resistance. The lightness (L ^* value) of the black light shielding plate was 33 to 36, indicating that the blackness was high.
Therefore, the black light-shielding plates of Examples 36 and 37 are extremely useful as shutter blade materials because they are excellent in light-shielding properties, low reflectivity, water repellency, slipperiness, and ultraviolet resistance.

On the other hand, the black light-shielding plate of Comparative Example 15 had an average optical density greater than 4.0 as in Examples 36 and 37, had a complete light-shielding property, and the arithmetic average height Ra of the film surface was 0.35 μm. However, the average regular reflectance was as high as 1.72%. The lightness (L ^* value) of the black light shielding plate was as high as 50, and the blackness was low. Moreover, the contact angles with respect to water were 80 ° and less than 90 °, and the dynamic friction coefficient was 0.23.
Therefore, the black light-shielding plate of Comparative Example 15 is inadequate as a shutter blade material because it has poor average regular reflectance, lightness (L ^* value), water repellency, and slipperiness.
Table 4 shows the type of substrate, film configuration, and evaluation results.

A titanium carbide film having a thickness of 100 nm was formed on the surface of a polyimide film having an arithmetic average height (Ra) of 0.90 μm and a thickness of 50 μm as a first-layer metal light-shielding film. Next, a film of Example 1 having a thickness of 105 nm was formed as a second film on the surface of the metal light-shielding film to produce a black light-shielding plate. In both cases, the first film having the same film thickness and the second film having the same film thickness are formed symmetrically on both surfaces of the polyimide film, so that the film-like black shading plate without warping is formed. Was made. The measurement results of the characteristics are shown in Table 4.

A titanium carbide film having a thickness of 100 nm was formed on the surface of a polyimide film having an arithmetic average height (Ra) of 0.90 μm and a thickness of 50 μm as a first-layer metal light-shielding film. Next, a film of Example 3 having a thickness of 105 nm was formed as a second film on the surface of the metal light-shielding film to produce a black light-shielding plate. In both cases, the first film having the same film thickness and the second film having the same film thickness are formed symmetrically on both surfaces of the polyimide film, so that the film-like black shading plate without warping is formed. Was made. The measurement results of the characteristics are shown in Table 4.

(Comparative Example 16)
In Comparative Example 16, a titanium carbide film (film thickness: 100 nm) was formed as a first-layer metal light-shielding film on the surface of a polyimide film having an arithmetic average height (Ra) of 0.90 μm and a thickness of 50 μm. A film of Comparative Example 1 having a thickness of 105 nm was formed as a second layer film on the surface of the light shielding film. The measurement results of the characteristics are shown in Table 4.

The produced black light shielding plates of Examples 38 and 39 both showed an average optical density greater than 4.0 at a wavelength of 380 to 780 nm and exhibited complete light shielding properties. The average regular reflectance was 0.21 to 0.31%, which was 0.8% or less. The arithmetic average height (Ra) of the film surface was 0.73 μm, and the contact angle with water was 110 to 120 °, indicating excellent water repellency. The dynamic friction coefficient was 0.10, and there was no deformation or discoloration of the film due to UV resistance. The lightness (L ^* value) of the black light shielding plate was 28 to 30, indicating that the blackness was high.
Therefore, the black light-shielding plates of Examples 38 and 39 are very useful as shutter blade materials because they are excellent in light-shielding properties, low reflectivity, water repellency, slipperiness, and ultraviolet resistance.

On the other hand, the black light-shielding plate of Comparative Example 16 had an average optical density greater than 4.0 as in Examples 38 and 39, had a complete light-shielding property, and the arithmetic average height Ra of the film surface was 0.73 μm. However, the average regular reflectance was 1.25%, which was higher than those in Examples 38 and 39. The lightness (L ^* value) of the black light shielding plate was as high as 47, and the blackness was low. Moreover, the contact angle with respect to water was 89 degrees and less than 90 degrees, and the dynamic friction coefficient was 0.24.
Therefore, the black light-shielding plate of Comparative Example 16 is not suitable as a shutter blade material because it has poor average regular reflectance, lightness (L ^* value), water repellency, and slipperiness.
Table 4 shows the type of substrate, film configuration, and evaluation results.

A titanium carbide film having a thickness of 40 nm was formed as a first-layer metal light-shielding film on the surface of a polyimide film having an arithmetic average height (Ra) of 0.90 μm and a thickness of 50 μm. Next, a film of Example 3 having a thickness of 105 nm was formed as a second film on the surface of the metal light-shielding film to produce a black light-shielding plate. In both cases, the first film having the same film thickness and the second film having the same film thickness are formed symmetrically on both surfaces of the polyimide film, so that the film-like black shading plate without warping is formed. Was made. The measurement results of the characteristics are shown in Table 4.

A titanium carbide film having a thickness of 200 nm was formed as a first-layer metal light-shielding film on the surface of a polyimide film having an arithmetic average height (Ra) of 0.90 μm and a thickness of 50 μm. Next, a film of Example 3 having a thickness of 105 nm was formed as a second film on the surface of the metal light-shielding film to produce a black light-shielding plate. In both cases, the first film having the same film thickness and the second film having the same film thickness are formed symmetrically on both surfaces of the polyimide film, so that the film-like black shading plate without warping is formed. Was made. The measurement results of the characteristics are shown in Table 4.

(Comparative Example 17)
A titanium carbide film having a thickness of 38 nm was formed as a first-layer metal light-shielding film on the surface of a polyimide film having an arithmetic average height (Ra) of 0.90 μm and a thickness of 50 μm. Next, a film of Example 3 having a thickness of 105 nm was formed as a second film on the surface of the metal light-shielding film to produce a black light-shielding plate. In both cases, the first film having the same film thickness and the second film having the same film thickness are formed symmetrically on both surfaces of the polyimide film, so that the film-like black shading plate without warping is formed. Was made. The measurement results of the characteristics are shown in Table 4.

The produced black light-shielding plates of Examples 40 and 41 both had an average optical density greater than 4.0 at wavelengths of 380 to 780 nm and exhibited complete light-shielding properties. The average regular reflectance was 0.31 to 0.36%, which was 0.8% or less. The arithmetic average height (Ra) of the film surface was 0.38 to 0.40 μm, and the water contact angle was 95 to 103 °, indicating excellent water repellency. The coefficient of dynamic friction was 0.09 to 0.10, and there was no deformation or discoloration of the film due to UV resistance. The lightness (L ^* value) of the black light shielding plate was 35 to 38, indicating that the blackness was high.
Therefore, the black light-shielding plates of Examples 40 and 41 are very useful as shutter blade materials because they are excellent in light-shielding properties, low reflectivity, water repellency, slipperiness, and ultraviolet resistance.

On the other hand, the black light-shielding plate of Comparative Example 17 had the same average regular reflectance, brightness (L ^* value), arithmetic average height Ra of the film, contact angle with water, and UV resistance as those of Examples 40 and 41. However, the average optical density was 3.89, which was not completely light-shielding, and the dynamic friction coefficient was as large as 0.20.
Therefore, the black light shielding plate of Comparative Example 17 is not suitable as a shutter blade material because it lacks light shielding properties and sliding properties.
Table 4 shows the type of substrate, film configuration, and evaluation results.

A titanium carbide film having a thickness of 100 nm was formed as a first-layer metal light-shielding film on the surface of a polyimide film having an arithmetic average height (Ra) of 0.25 μm and a thickness of 38 μm. Next, as a second layer film on the surface of the metal light-shielding film, the film of Example 3 was formed with a thickness of 20 nm (a black light-shielding plate was produced. Both were the same film on both sides of the polyimide film. A film-shaped black light-shielding plate without warpage was produced by symmetrically forming a first-layer film having the same thickness and a second-layer film having the same type and the same film thickness. This is shown in FIG.

A titanium carbide film having a thickness of 100 nm was formed as a first-layer metal light-shielding film on the surface of a polyimide film having an arithmetic average height (Ra) of 0.25 μm and a thickness of 38 μm. Next, as a second layer film on the surface of the metal light-shielding film, the film of Example 3 was formed with a thickness of 53 nm to produce a black light-shielding plate. In both cases, the first film having the same film thickness and the second film having the same film thickness are formed symmetrically on both surfaces of the polyimide film, so that the film-like black shading plate without warping is formed. Was made. The measurement results of the characteristics are shown in Table 4.

A titanium carbide film having a thickness of 100 nm was formed as a first-layer metal light-shielding film on the surface of a polyimide film having an arithmetic average height (Ra) of 0.25 μm and a thickness of 38 μm. Next, as a second layer film on the surface of the metal light-shielding film, the film of Example 3 was formed with a thickness of 200 nm to produce a black light-shielding plate. In both cases, the first film having the same film thickness and the second film having the same film thickness are formed symmetrically on both surfaces of the polyimide film, so that the film-like black shading plate without warping is formed. Was made. The measurement results of the characteristics are shown in Table 4.

(Comparative Example 18)
A titanium carbide film having a thickness of 100 nm was formed as a first-layer metal light-shielding film on the surface of a polyimide film having an arithmetic average height (Ra) of 0.25 μm and a thickness of 38 μm. Next, as a second layer film on the surface of the metal light-shielding film, the film of Example 3 was formed with a thickness of 17 nm to produce a black light-shielding plate. In both cases, the first film having the same film thickness and the second film having the same film thickness are formed symmetrically on both surfaces of the polyimide film, so that the film-like black shading plate without warping is formed. Was made. The measurement results of the characteristics are shown in Table 4.

Each of the produced black light shielding plates of Examples 42 to 44 had an average optical density greater than 4.0 at a wavelength of 380 to 780 nm, and exhibited complete light shielding properties. The average regular reflectance was 0.43 to 0.73%, which was 0.8% or less. The arithmetic average height (Ra) of the film surface was 0.20 μm for all, and the water contact angle was 105 to 107 °, indicating excellent water repellency. The dynamic friction coefficient was 0.10, and there was no deformation or discoloration of the film due to UV resistance. The lightness (L ^* value) of the black light shielding plate was 43 to 45, indicating that the blackness was high.
Therefore, the black light shielding plates of Examples 42 to 44 are very useful as shutter blade materials because they are excellent in light shielding properties, low reflectivity, water repellency, slipperiness, and ultraviolet resistance.

On the other hand, the black light-shielding plate of Comparative Example 18 had an average optical density, an arithmetic average height Ra of the film, a contact angle with water, and an ultraviolet resistance that were the same as those of Examples 42 to 44, but the average regular reflectance was high. Also, the lightness (L ^* value) was insufficient in blackness.
Therefore, the black light-shielding plate of Comparative Example 18 is not suitable as a shutter blade material because the average regular reflectance is poor and the blackness is insufficient.
Table 4 shows the type of substrate, film configuration, and evaluation results.

A titanium carbide oxide film having a thickness of 100 nm was formed as a first-layer metal light-shielding film on the surface of a polyimide film having an arithmetic average height (Ra) of 0.90 μm and a thickness of 50 μm. Next, as a second layer film on the surface of the metal light shielding film, the film of Example 1 was formed to a thickness of 105 nm to produce a black light shielding plate. In both cases, the first film having the same film thickness and the second film having the same film thickness are formed symmetrically on both surfaces of the polyimide film, so that the film-like black shading plate without warping is formed. Was made. The measurement results of the characteristics are shown in Table 4.

A titanium carbide oxide film having a thickness of 100 nm was formed as a first-layer metal light-shielding film on the surface of a polyimide film having an arithmetic average height (Ra) of 0.90 μm and a thickness of 50 μm. Next, as a second layer film on the surface of the metal light shielding film, the film of Example 2 was formed to a thickness of 105 nm to produce a black light shielding plate. In both cases, the first film having the same film thickness and the second film having the same film thickness are formed symmetrically on both surfaces of the polyimide film, so that the film-like black shading plate without warping is formed. Was made. The measurement results of the characteristics are shown in Table 4.

A titanium carbide oxide film having a thickness of 100 nm was formed as a first-layer metal light-shielding film on the surface of a polyimide film having an arithmetic average height (Ra) of 0.90 μm and a thickness of 50 μm. Next, a film of Example 3 having a thickness of 105 nm was formed as a second layer on the surface of the metal light-shielding film to produce a black light-shielding plate. In both cases, the first film having the same film thickness and the second film having the same film thickness are formed symmetrically on both surfaces of the polyimide film, so that the film-like black shading plate without warping is formed. Was made. The measurement results of the characteristics are shown in Table 4.

Each of the produced black light shielding plates of Examples 45 to 47 had an average optical density greater than 4.0 at a wavelength of 380 to 780 nm, and exhibited complete light shielding properties. The average regular reflectance was 0.20 to 0.50%, which was 0.8% or less. The arithmetic average height (Ra) of the film surface was 0.75 μm for all, and the water contact angle was 96 to 113 °, indicating excellent water repellency. The coefficient of dynamic friction was 0.10 or less, and there was no deformation or discoloration of the film due to UV resistance. The lightness (L ^* value) of the black light shielding plate was 34 to 42, indicating that the blackness was high.
Therefore, the black light-shielding plates of Examples 45 to 47 are very useful as shutter blade materials because they are excellent in light-shielding properties, low reflectivity, water repellency, slipperiness and ultraviolet resistance.
Table 4 shows the type of substrate, film configuration, and evaluation results.

(Comparative Example 19)
The film type, thickness and surface roughness, and the film type and film thickness of the first and second layers, except that the film was formed in a stationary state when the second layer film was formed By forming a first layer film of the same film thickness and a second layer film of the same type and the same film thickness on both sides of the same polyimide film as in Example 43, a film-like black color without warping A light shielding plate was produced. The measurement results of the characteristics are shown in Table 4.

The produced black light shielding plates of Comparative Example 19 all had an average optical density of greater than 4.0 at a wavelength of 380 to 780 nm, exhibited complete light shielding properties, and good ultraviolet resistance. However, the average regular reflectance is 0.9%, the lightness L ^* is 49, the arithmetic average height (Ra) of the film surface is 0.13 μm, the dynamic friction coefficient is 0.18, and the contact angle with water is 70 °. The characteristic was worse than Example 43 of the same structure except the conditions at the time of film-forming of a 2nd layer differing. Further, the adhesion of the film was evaluated based on JIS C0021, but a part of the film was peeled off at the interface with the underlying TiC film, and the adhesion was poor. As a result of evaluation with a scanning X-ray photoelectron spectrometer, the C / Ti atom number ratio in the film thickness direction of the second layer is 31.00 and the O / Ti atom number ratio is 0.54, both uniform in the film thickness direction. Met.
Therefore, the black light-shielding plate of Comparative Example 19 is excellent in light-shielding properties and UV resistance, but has poor reflectance, brightness, water repellency, slipperiness, and film adhesion, so that it is a shutter blade material used under high temperature and high humidity. Cannot be used.

Using a NiTi target (containing 3 wt% Ti) on the surface of a polyimide film having a surface arithmetic average height (Ra) of 0.25 μm and a thickness of 25 μm, a NiTi film (Ti content 2.98 wt%) A metal light-shielding film was formed with a thickness of 110 nm, and a black light-shielding plate was produced in the same manner as in Example 3.
The metal light shielding film was formed by a direct current sputtering method with a deposition gas pressure of 0.3 Pa.
Next, the film of Example 3 was formed to a thickness of about 105 nm as the second layer film.
In both cases, a film-shaped black shading plate without warping is produced by symmetrically forming a first layer film of the same thickness and a second layer film of the same type and thickness on both sides of the film. did.
The measurement results of the characteristics are shown in Table 5.

A metal light-shielding film of a Cu film having a thickness of 110 nm is formed on the surface of a polyimide film having a surface arithmetic average height (Ra) of 0.25 μm and a thickness of 25 μm using a Cu target, as in Example 3. Thus, a black light shielding plate was produced.
The metal light shielding film was formed by a direct current sputtering method with a deposition gas pressure of 0.3 Pa.
Next, the film of Example 3 was formed to a thickness of about 105 nm as the second layer film.
In both cases, a film-shaped black shading plate without warping is produced by symmetrically forming a first layer film of the same thickness and a second layer film of the same type and thickness on both sides of the film. did.
Table 5 shows the characteristics.

An arithmetical average height (Ra) of the surface is 0.25 μm, and a metal light-shielding film of Al film is formed to a thickness of 110 nm using an Al target on the surface of a polyimide film having a thickness of 25 μm. Thus, a black light shielding plate was produced.
The metal light shielding film was formed by a direct current sputtering method with a deposition gas pressure of 0.3 Pa.
Next, the film of Example 3 was formed to a thickness of about 105 nm as the second layer film.
In both cases, a film-shaped black shading plate without warping is produced by symmetrically forming a first layer film of the same thickness and a second layer film of the same type and thickness on both sides of the film. did.
Table 5 shows the characteristics.

Using a Ti target on the surface of a polyimide film having a surface arithmetic average height (Ra) of 0.25 μm and a thickness of 25 μm, a metal light-shielding film of Ti film is formed only by 110 nm. A black shading plate was produced.
The metal light shielding film was formed by a direct current sputtering method with a deposition gas pressure of 0.3 Pa.
Next, the film of Example 3 was formed to a thickness of about 105 nm as the second layer film.
In both cases, a film-shaped black shading plate without warping is produced by symmetrically forming a first layer film of the same thickness and a second layer film of the same type and thickness on both sides of the film. did.
Table 5 shows the characteristics.

Using a Ti target on the surface of a polyimide film having a surface arithmetic average height (Ra) of 0.25 μm and a thickness of 25 μm, a metal light-shielding film of Ti film is formed only by 110 nm. A black shading plate was produced.
The metal light shielding film was formed by a direct current sputtering method with a deposition gas pressure of 0.3 Pa.
Next, the film of Example 8 was formed to a thickness of about 105 nm as the second layer film.
In both cases, a film-shaped black shading plate without warping is produced by symmetrically forming a first layer film of the same thickness and a second layer film of the same type and thickness on both sides of the film. did.
Table 5 shows the characteristics.

The average regular reflectance of the obtained black light shielding plate was 0.29 to 0.48% in Examples 48 to 52, and the reflection was low. The average optical density was all greater than 4.0 and had complete light shielding properties. The arithmetic average height Ra of the film surface is 0.20 μm, the contact angle with water is 100 to 124 °, the lightness (L ^* value) is 30 to 37, the dynamic friction coefficient is 0.1, and the UV resistance is deformation of the film. No discoloration was seen.
Therefore, the black light-shielding plates of Examples 48 to 52 are very useful as shutter blade materials because they are excellent in light-shielding properties, low reflectivity, water repellency, slipperiness, and ultraviolet resistance.

(Comparative Example 20)
Using a NiTi target (containing 3 wt% Ti) on the surface of a polyimide film having a surface arithmetic average height (Ra) of 0.25 μm and a thickness of 25 μm, a metal of NiTi film (Ti content 2.98 wt%) A light shielding film having a thickness of 110 nm was formed, and a black light shielding plate was produced in the same manner as in Example 48.
The metal light shielding film was formed by the direct current sputtering method under the sputtering film formation conditions (film formation gas pressure) shown in Example 48.
Next, a film of Comparative Example 1 having a thickness of about 105 nm was formed as a second layer film. The measurement results of the characteristics are shown in Table 5.

(Comparative Example 21)
Using a Cu target, a metal light-shielding film of Cu film having a thickness of 110 nm was formed on the surface of a polyimide film having a surface arithmetic average height (Ra) of 0.25 μm and a thickness of 25 μm. Thus, a black light shielding plate was produced.
The metal light shielding film was formed by the direct current sputtering method under the sputtering film formation conditions (film formation gas pressure) shown in Example 49.
Next, the film of Comparative Example 1 was formed to a thickness of about 105 nm as the second layer film. The measurement results of the characteristics are shown in Table 5.

(Comparative Example 22)
On the surface of a polyimide film having a surface arithmetic average height (Ra) of 0.25 μm and a thickness of 25 μm, a metal light-shielding film of Al film is formed to a thickness of 110 nm using an Al target. A black shading plate was produced.
The metal light shielding film was formed by the direct current sputtering method under the sputtering film formation conditions (film formation gas pressure) shown in Example 50.
Next, the film of Comparative Example 1 was formed to a thickness of about 105 nm as the second layer film. The measurement results of the characteristics are shown in Table 5.

(Comparative Example 23)
Using a Ti target on the surface of a polyimide film having an arithmetic average height (Ra) of 0.25 μm and a thickness of 25 μm, a metal light-shielding film of Ti film having a thickness of 110 nm was formed in the same manner as in Example 51. Thus, a black light shielding plate was produced.
The metal light-shielding film was formed by the direct current sputtering method under the sputtering film formation conditions (film formation gas pressure) shown in Example 51.
Next, the film of Comparative Example 1 was formed to a thickness of about 105 nm as the second layer film. The measurement results of the characteristics are shown in Table 5.

In both cases, a film-shaped black shading plate without warping is produced by symmetrically forming a first layer film of the same thickness and a second layer film of the same type and thickness on both sides of the film. did.
Each of the obtained black light shielding plates had an average optical density at a wavelength of 380 to 780 nm of greater than 4.0 and exhibited complete light shielding properties. The average regular reflectance at wavelengths of 380 to 780 nm was 1.17 to 1.57% in Comparative Examples 20 to 23, the L ^* value was as high as 48 to 52, and the black light shielding plate had a low blackness.

Further, the arithmetic average height Ra on the film surface was 0.20 μm, and the UV resistance was good without any discoloration or deformation, but the water contact angle was 76 to 86 ° and the water repellency was small. The coefficient of dynamic friction was as large as 0.21 to 0.31 and was found to be inferior in slipperiness.
Therefore, although the black light shielding plates of Comparative Examples 20 to 23 have complete light shielding properties and ultraviolet resistance, they are not suitable as shutter blade materials because of poor reflectivity, water repellency, and slipperiness.

On the surface of a PET film having a surface arithmetic average height (Ra) of 0.42 μm and a thickness of 75 μm, the types, film thicknesses, and film forming conditions of the first and second layers are as in Example 48. Similarly, a black light shielding plate was produced. The measurement results of the characteristics are shown in Table 5.

On the surface of a PET film having a surface arithmetic average height (Ra) of 0.42 μm and a thickness of 75 μm, the types, film thicknesses, and film forming conditions of the first and second layers are as in Example 49. Similarly, a black light shielding plate was produced. The measurement results of the characteristics are shown in Table 5.

On the surface of a PET film having a surface arithmetic average height (Ra) of 0.42 μm and a thickness of 75 μm, the types, film thicknesses, and film forming conditions of the first and second layers are as in Example 50. Similarly, a black light shielding plate was produced. The measurement results of the characteristics are shown in Table 5.

On the surface of a PET film having a surface arithmetic average height (Ra) of 0.42 μm and a thickness of 75 μm, the types, film thicknesses, and film forming conditions of the first and second layers are as in Example 51. Similarly, a black light shielding plate was produced. The measurement results of the characteristics are shown in Table 5.

In both cases, a film-shaped black light-shielding plate having no warp was produced by symmetrically forming a first layer film of the same thickness and a second layer film of the same type and thickness on both sides of the film. .
Each of the obtained black light shielding plates had an average optical density at a wavelength of 380 to 780 nm of greater than 4.0 and exhibited complete light shielding properties. Further, the average specular reflectance at wavelengths of 380 to 780 nm was very low reflection of 0.23 to 0.30% in Examples 53 to 56, the L ^* value was also low to 32 to 35, and black color was exhibited. .
Further, the arithmetic average height Ra of the film surface was 0.38 μm, the contact angle with water was 99 to 110 °, the dynamic friction coefficient was 0.1 or less, and no deformation or discoloration of the film was observed in the ultraviolet resistance.
Therefore, the black light shielding plates of Examples 53 to 56 are extremely useful as shutter blade materials because they are excellent in light shielding properties, low reflection properties, water repellency, slipperiness, and ultraviolet resistance.

(Comparative Example 24)
A black light-shielding plate was produced in the same manner as in Example 53 except that the second layer film was changed to the film of Comparative Example 1. The measurement results of the characteristics are shown in Table 5.

(Comparative Example 25)
A black light-shielding plate was produced in the same manner as in Example 54 except that the second layer film was changed to the film of Comparative Example 1. The measurement results of the characteristics are shown in Table 5.

(Comparative Example 26)
A black light-shielding plate was produced in the same manner as in Example 55 except that the second layer film was changed to the film of Comparative Example 1. The measurement results of the characteristics are shown in Table 5.

(Comparative Example 27)
A black light-shielding plate was produced in the same manner as in Example 56 except that the second layer film was changed to the film of Comparative Example 1. The measurement results of the characteristics are shown in Table 5.

Each of the obtained black light shielding plates had an average optical density at a wavelength of 380 to 780 nm of greater than 4.0 and exhibited complete light shielding properties. The average regular reflectance at wavelengths of 380 to 780 nm was 1.56 to 1.95% in Comparative Examples 24 to 27, the L ^* value was as high as 50 to 52, and the black light shielding plate had a low blackness.
The arithmetic average height Ra of the film surface was 0.38 μm, and the UV resistance was good without any discoloration or deformation, but the water contact angle was 74 to 86 ° and the water repellency was small. . The coefficient of dynamic friction was as large as 0.21 to 0.28, indicating that the slipperiness was poor.
Therefore, although the black light shielding plates of Comparative Examples 24 to 27 have complete light shielding properties and ultraviolet resistance, they are unsuitable as shutter blade materials because of poor reflectivity, water repellency, and slipperiness.

On the surface of the PEN film having a surface arithmetic average height (Ra) of 0.90 μm and a thickness of 100 μm, the types, film thicknesses, and film forming conditions of the first and second layers are as in Example 48. Similarly, a black light shielding plate was produced. The measurement results of the characteristics are shown in Table 5.

On the surface of the PEN film having a surface arithmetic average height (Ra) of 0.90 μm and a thickness of 100 μm, the types, film thicknesses, and film forming conditions of the first and second layers are as in Example 49. Similarly, a black light shielding plate was produced. The measurement results of the characteristics are shown in Table 5.

On the surface of a PEN film having a surface arithmetic average height (Ra) of 0.90 μm and a thickness of 100 μm, the types, film thicknesses, and film forming conditions of the first and second layers are as in Example 50. Similarly, a black light shielding plate was produced. The measurement results of the characteristics are shown in Table 5.

On the surface of a PEN film having a surface arithmetic average height (Ra) of 0.90 μm and a thickness of 100 μm, the types, film thicknesses, and film forming conditions of the first and second layers are as in Example 51. Similarly, a black light shielding plate was produced. The measurement results of the characteristics are shown in Table 5.

In both cases, a film-shaped black light-shielding plate having no warp was produced by symmetrically forming a first layer film of the same thickness and a second layer film of the same type and thickness on both sides of the film. .
Each of the obtained black light shielding plates had an average optical density at a wavelength of 380 to 780 nm of greater than 4.0 and exhibited complete light shielding properties. Further, the average regular reflectance at wavelengths of 380 to 780 nm is very low reflection of 0.21 to 0.32% in Examples 57 to 60, the L ^* value is also low to 32 to 34, and black color is exhibited. It was.
In addition, the arithmetic average height Ra of the film surface was 0.68 μm, the contact angle with water was 103 to 110 °, the dynamic friction coefficient was 0.1, and no deformation or discoloration of the film was observed with respect to UV resistance.
Therefore, the black light shielding plates of Examples 57 to 60 are very useful as shutter blade materials because they have high blackness and are excellent in light shielding properties, low reflection properties, water repellency, slipping properties, and ultraviolet resistance.

(Comparative Example 28)
A black light-shielding plate was produced in the same manner as in Example 57 except that the second layer film was changed to the film of Comparative Example 1. The measurement results of the characteristics are shown in Table 5.

(Comparative Example 29)
A black light-shielding plate was produced in the same manner as in Example 58 except that the second layer film was changed to the film of Comparative Example 1. The measurement results of the characteristics are shown in Table 5.

(Comparative Example 30)
A black light-shielding plate was produced in the same manner as in Example 59 except that the second layer film was changed to the film of Comparative Example 1. The measurement results of the characteristics are shown in Table 5.

(Comparative Example 31)
A black light-shielding plate was produced in the same manner as in Example 60 except that the second layer film was changed to the film of Comparative Example 1. The measurement results of the characteristics are shown in Table 5.

Each of the obtained black light shielding plates had an average optical density at a wavelength of 380 to 780 nm of greater than 4.0 and exhibited complete light shielding properties. Further, the average regular reflectance at wavelengths of 380 to 780 nm was 1.06 to 1.37% in Comparative Examples 28 to 31, and the L ^* value was 46 to 47, which was a black light shielding plate with low blackness.
Further, the arithmetic average height Ra of the film surface was 0.68 μm. Its UV resistance was good with no discoloration or deformation, but the water contact angle was 75-86 °, water repellency was small, and the coefficient of dynamic friction was large, 0.25-0.28. I understood.
Therefore, although the black light shielding plates of Comparative Examples 28 to 31 have complete light shielding properties and UV resistance, they are unsuitable as shutter blade materials because of their low blackness and poor reflectivity, water repellency, and slipperiness. .

On the surface of a SUS thin plate having a surface arithmetic average height (Ra) of 0.24 μm and a thickness of 50 μm, a film gas pressure of 0.3 Pa and a TiC film of 110 nm were formed as a first layer film. . Next, a black light-shielding plate in which the film of Example 3 was formed with a thickness of 105 nm was prepared as the second layer film. The measurement results of the characteristics are shown in Table 5.

(Comparative Example 32)
On the surface of a SUS thin plate having a surface arithmetic average height (Ra) of 0.24 μm and a thickness of 50 μm, a film gas pressure of 0.3 Pa and a TiC film of 110 nm were formed as a first layer film. . Next, a black light-shielding plate in which the film of Comparative Example 1 was formed to a thickness of 105 nm was prepared as the second layer film. The measurement results of the characteristics are shown in Table 5.

In both cases, a film-shaped black light-shielding plate having no warp was produced by symmetrically forming a first layer film of the same thickness and a second layer film of the same type and thickness on both sides of the film. .
In each case, the obtained black light shielding plate had an average optical density at a wavelength of 380 to 780 nm larger than 4.0, and exhibited a complete light shielding property. Further, the average regular reflectance at wavelengths of 380 to 780 nm was as low as 0.58% in Example 61, the L ^* value was as low as 43, and black color was exhibited. Further, the arithmetic average height Ra of the film surface was 0.20 μm, the contact angle with water was 93 °, the dynamic friction coefficient was 0.1, and no deformation or discoloration of the film was observed with respect to UV resistance.
Therefore, the black light shielding plate of Example 61 is very useful as a shutter blade material because it has high blackness and is excellent in light shielding properties, low reflectivity, water repellency, slipperiness, and ultraviolet resistance.

On the other hand, in Comparative Example 32, the average optical density was higher than 4.0, but the average regular reflectance was as high as 1.42%, the lightness (L ^* value) was 48, and the blackness was low.
The arithmetic average height Ra of the film surface was 0.20 μm, the contact angle with water was 85 °, the dynamic friction coefficient was 0.26, and the film was neither deformed nor discolored with respect to UV resistance.
Therefore, although the black light shielding plate of Comparative Example 32 has good light shielding properties and UV resistance, it is unsuitable as a shutter blade material because it has low blackness and low reflectivity, water repellency, and slipperiness.

A black polyimide film having a surface arithmetic average height Ra of 0.40 μm and a thickness of 38 μm was used as the type of base material, the thickness of the first TiC film was 50 nm, and the second layer film of Example 3 was used. A black shading plate having a film thickness of 200 nm was prepared. The measurement results of the characteristics are shown in Table 5.

A black polyimide film having a surface arithmetic average height Ra of 0.40 μm and a thickness of 38 μm was used as the type of base material, the thickness of the first TiC film was 50 nm, and the second layer film of Example 3 was used. A black shading plate having a film thickness of 20 nm was prepared. The measurement results of the characteristics are shown in Table 5.

(Comparative Example 33)
A black polyimide film having a surface arithmetic average height Ra of 0.40 μm and a thickness of 38 μm was used as the type of base material, the thickness of the first TiC film was 50 nm, and the second layer film of Example 3 was used. A black shading plate having a film thickness of 18 nm was prepared. The measurement results of the characteristics are shown in Table 5.

(Comparative Example 34)
A black polyimide film having a surface arithmetic average height Ra of 0.40 μm and a thickness of 38 μm was used as the type of base material, the thickness of the first TiC film was 50 nm, and the second layer film of Example 3 was used. A black shading plate having a film thickness of 213 nm was produced. The measurement results of the characteristics are shown in Table 5.

The black light-shielding plate of Example 62 had an average optical density at wavelengths of 380 to 780 nm of greater than 4.0, and exhibited complete light-shielding properties. Further, the average regular reflectance was as low as 0.34%, and the lightness (L ^* value) was 31 and the blackness was high.
The arithmetic average height Ra of the film surface was 0.30 μm, the contact angle with water was 94 °, the dynamic friction coefficient was 0.07, and no deformation or discoloration of the film was observed with respect to UV resistance.

As for Example 63, as shown in Table 5, the average regular reflectance was as low as 0.37%, lightness (L ^* value) was 40, which was lower than that of Example 61, and blackness was high. The characteristics were the same as in Example 61.
Therefore, the black light shielding plates of Examples 62 to 63 are very useful as shutter blade materials because of their high blackness and excellent light shielding properties, low reflectivity, water repellency, slipperiness, and ultraviolet resistance.

On the other hand, the black light-shielding plate of Comparative Example 33 had an average optical density of 3.5 and was not completely light-shielding. Moreover, it was found that the dynamic friction coefficient was as large as 0.25 and the slipperiness was poor.

In Comparative Example 34, each characteristic was the same as that in Example 62. However, the thickness of the second layer was increased, and the film formation rate of the diamond-like carbon (DLC) gradient structure black coating film was small, so that it was thicker than 200 nm. Then, the sputtering time becomes very long, a problem in terms of manufacturing cost and a sputtering start time due to the batch are generated, and the routine cannot be made. It is inappropriate as a shutter blade material.
Therefore, although the black light shielding plate of Comparative Example 33 has UV resistance, it is inadequate as a shutter blade material because of its poor light shielding properties, and the black light shielding plate of Comparative Example 34 has good characteristics. Since the second layer is thick, there is a problem in terms of manufacturing cost.

A black light-shielding plate was produced in the same manner as in Example 62 except that the base material was changed to a black PET film having a surface arithmetic average height Ra of 0.40 μm and a thickness of 38 μm. The measurement results of the characteristics are shown in Table 5.

The first layer is the same except that the base material is changed to a black PET film having an arithmetic average height Ra of 0.40 μm and a thickness of 38 μm, and the film thickness of the second layer is changed to 20 nm. A black light-shielding plate was produced in the same manner as in Example 63 with respect to the type and thickness of the film. The measurement results of the characteristics are shown in Table 5.

(Comparative Example 35)
A black light shielding plate was produced in the same manner as in Comparative Example 33, except that the type of substrate was changed to a black PET film having a surface arithmetic average height Ra of 0.40 μm and a thickness of 38 μm. The measurement results of the characteristics are shown in Table 5.

(Comparative Example 36)
A black light-shielding plate was produced in the same manner as in Comparative Example 34 except that the type of the substrate was changed to a black PET film having a surface arithmetic average height Ra of 0.40 μm and a thickness of 38 μm. The measurement results of the characteristics are shown in Table 5.

The black light-shielding plate of Example 64 had an average optical density at wavelengths of 380 to 780 nm of greater than 4.0, and exhibited complete light-shielding properties. Further, the average regular reflectance was as low as 0.35%, and the lightness (L ^* value) was 32 and the blackness was high.
The arithmetic average height Ra of the film surface was 0.30 μm, the contact angle with water was 93 °, the dynamic friction coefficient was 0.09, and the film was neither deformed nor discolored with respect to UV resistance.

The characteristics of Example 65 were substantially the same as those of Example 64 except that the brightness (L ^* value) was as high as 40 as shown in the table.
Therefore, the black light shielding plates of Examples 64 to 65 are very useful as shutter blade materials because they have high blackness and are excellent in light shielding properties, low reflection properties, water repellency, slipping properties, and ultraviolet resistance.

On the other hand, the black light-shielding plate of Comparative Example 35 had an average optical density of 3.4 and was not completely light-shielding. Moreover, it was found that the coefficient of dynamic friction was as large as 0.24 and the slipperiness was poor.
Therefore, although the black light-shielding plate of Comparative Example 35 has ultraviolet resistance, it is inadequate as a shutter blade material because of its poor light-shielding properties.

In Comparative Example 36, each characteristic was the same as that in Example 64. However, since the deposition rate of the second diamond-like carbon (DLC) gradient structure black coating film was small, the sputtering time was very large when the thickness was greater than 200 nm. Since it becomes long, a problem in terms of manufacturing cost and a sputtering start time between batches occur, and it becomes impossible to make a routine, so it is not suitable as a shutter blade material.

DESCRIPTION OF SYMBOLS 1 Base material 1a Colorable base material 2 Diamond-like carbon (DLC) gradient structure black coating film 3 Metal light shielding film 11 Resin film base material 12 Unwinding roll 13 Vacuum pump 14 Vacuum tank 15 Cooling can roll 16 Winding roll 17 Magnetron cathode 18 Target 19 Bulkhead

Claims

A diamond-like carbon gradient structure black coating film (A) containing titanium, carbon, and oxygen, formed by sputtering,
The diamond-like carbon gradient structure black coating film (A) has a carbon content of 2.0 to 30.0 as a C / Ti atomic ratio.
The oxygen content is 0.8 to 2.2 as the O / Ti atomic ratio,
And C / Ti atomic ratio and O / Ti atomic ratio have the structure which changed continuously in the film thickness direction,
The diamond-like carbon gradient structure black coating film, wherein the diamond-like carbon gradient structure black coating film (A) has a thickness of 20 nm or more.
2. The oxygen and titanium contents increase and the carbon contents decrease in the film thickness direction from the film surface on the sputtering side of the diamond-like carbon gradient structure black coating film (A). The diamond-like carbon gradient structure black coating film described in 1.
3. The diamond-like carbon gradient structure black coating film according to claim 1, wherein the diamond-like carbon gradient structure black coating film (A) has a thickness of 20 to 200 nm.
The diamond-like carbon according to any one of claims 1 to 3, wherein the composition of carbon in the diamond-like carbon gradient structure black coating film (A) is a mixture of sp2-bonded carbon and sp3-bonded carbon. Carbon gradient structure black coating film.
5. The diamond-like carbon gradient structure black coating film according to claim 1, which has a static contact angle with respect to water of 90 ° or more.
The diamond-like carbon gradient structure black coating film according to any one of claims 1 to 5, wherein a coefficient of dynamic friction is 0.1 or less.
The diamond-like carbon gradient structure black coating according to any one of claims 1 to 6, wherein an arithmetic average height Ra in a region of 1 µm x 1 µm measured by an atomic force microscope is 0.8 nm or more. Covering.
8. The parallel light transmittance at a wavelength of 380 to 780 nm of a diamond-like carbon gradient structure black coating film formed on a glass substrate by a sputtering method has an average value of 20 to 50%. A diamond-like carbon gradient structure black coating film according to claim 1.
Sputtering is performed at a deposition gas pressure of 1.5 Pa or more using a sputtering target selected from a combination of a titanium sintered body and a carbon sintered body, or a combination of a titanium carbide sintered body and a carbon sintered body. A method for producing a diamond-like carbon gradient structure black coating film, comprising forming a diamond-like carbon gradient structure black coating film thereon.
Using a target selected from a combination of a titanium sintered body and a carbon sintered body, or a combination of a titanium carbide sintered body and a carbon sintered body, sputtering is performed with a dual magnetron cathode or a double magnetron cathode, and diamond-like is formed on the substrate. The method for producing a diamond-like carbon gradient structure black coating film according to claim 9, wherein the carbon gradient structure black coating film is formed.
Using a target selected from a combination of a titanium sintered body and a carbon sintered body, or a combination of a titanium carbide sintered body and a carbon sintered body, without introducing oxygen gas as a film forming gas during film formation, argon, Alternatively, sputtering is performed by introducing an inert gas mainly containing helium, and oxygen contained in the sintered body, oxygen in the residual gas in the deposition chamber, or both are taken into the film. A method for producing a diamond-like carbon gradient structure black coating film according to any one of claims 9 and 10.
A black light shielding plate composed of a base material (B), a metal light shielding film (C), and a black coating film,
The substrate (B) is a resin film, resin plate, metal thin plate, ceramic thin plate having fine irregularities on the surface,
A metal light-shielding film (C) having a film thickness of 40 nm or more provided on at least one surface of the substrate (B),
The black coating film provided on the surface of the metal light-shielding film (C) is the diamond-like carbon gradient structure black coating film (A) according to any one of claims 1 to 8. Shading plate.
The base material (B) is any one selected from stainless steel, SK (carbon steel), Al, Ti metal thin plate, alumina, magnesia, silica, zirconia ceramic thin plate, glass plate, resin plate, and resin film. The black light-shielding plate according to claim 12.
The resin film is any one selected from polyimide, polyamideimide, polyetheretherketone, polyethylene terephthalate, polyphenylene sulfide, polyethylene naphthalate, polyethersulfone, and polycarbonate having a thickness of 5 to 200 μm. The black light shielding plate according to claim 13.
The metal light-shielding film (C) is a metal material containing as a main component one or more elements selected from titanium, tantalum, tungsten, cobalt, nickel, niobium, iron, zinc, copper, aluminum, or silicon. The black light-shielding plate according to claim 12, wherein:
The black light shielding plate according to any one of claims 12 to 15, wherein the metal light shielding film (C) is any one of a titanium film, a titanium carbide film, and a titanium carbide oxide film.
A metal light-shielding film (C) having the same film thickness and the same composition is provided on both surfaces of a substrate of a resin film, a resin plate, a metal thin plate, or a ceramic thin plate, and the same on the surface of the metal light-shielding film (C). The diamond-like carbon gradient structure black coating film (A) having a film thickness and the same composition is laminated and has a symmetrical structure with the base material as a center. Black shading plate.
The arithmetic average height Ra of the diamond-like carbon gradient structure black coating film (A) formed on the surface of the metal light-shielding film (C) is 0.2 to 0.7 μm,
18. The black regular reflection coefficient of the surface of the diamond-like carbon gradient structure black coating film (A) at a wavelength of 380 to 780 nm is 0.8% or less. Shading plate.
The lightness (L * ) of the black light-shielding plate in which the diamond-like carbon gradient structure black coating film (A) is provided on the surface of the metal light-shielding film (C) is 25 to 45. To 18. The black light shielding plate according to any one of 18 to 18.
A colored resin film is used as the substrate (B), the metal light-shielding film (C) is provided on at least one surface thereof, and the surface of the metal light-shielding film (C) is any one of claims 1 to 10. A black shading plate provided with the diamond-like carbon gradient structure black coating film (A) according to the description,
The diamond-like carbon gradient structure black coating film (A) has a thickness of 20 nm or more,
A black light shielding plate having an average specular reflectance of 1% or less on the surface of the black light shielding plate at a wavelength of 380 to 780 nm.
21. The black light shielding plate according to claim 20, wherein the colored resin film has surface unevenness.
The black light shielding plate according to claim 20 or 21, wherein the diamond-like carbon gradient structure black coating film (A) has a thickness of 20 to 200 nm.
The black light-shielding plate according to any one of claims 20 to 22, wherein the metal light-shielding film (C) has a thickness of 20 to 200 nm.
Lightness (L * ) of a black light-shielding plate provided with a metal light-shielding film (C) on the colored resin film and a diamond-like carbon gradient structure black coating film (A) on the surface of the metal light-shielding film (C) The black light-shielding plate according to any one of claims 20 to 23, wherein is from 25 to 45.
25. The black light shielding plate according to claim 20, wherein the colored resin film has a thickness of 20 to 200 μm.
A shutter blade obtained by punching the black light-shielding plate according to any one of claims 12 to 25.