JP5418802B2 - Member having segment-shaped inorganic material film and method for producing segment-shaped inorganic material film - Google Patents

Description

  The present invention relates to a member having a segment-shaped inorganic material film on a substrate and a method for producing a segment-shaped inorganic material film.

A diamond-like carbon (DLC) film effective for improving surface properties such as wear resistance improvement of a substrate surface is a tribology of the DLC film by coating it in a segment form instead of coating the whole surface of the substrate. It is known that (frictional wear) characteristics can be further improved, and peeling of the DLC film can be effectively prevented (see Patent Documents 1 and 2). The improvement in tribological properties is due to several features of the segment structure. One is suppression of abrasive wear due to wear powder. This technology is applied to grinding wheels. This is a method of creating a gap (groove) that can take in wear powder and suppressing abrasive wear. Second, the progress of film peeling can be suppressed. Since the film is cut between the segments, even if the film is peeled off in one segment, the adjacent segment is not affected. This suppresses the progress of peeling and prolongs the life of the film. And finally, the improvement of the adhesion. The main reason for improving the adhesion is that a large strain applied to the film accompanying the deformation of the substrate can be avoided. This is because the amount of deformation of DLC can be relaxed between segments, thereby reducing the shear stress applied to the film.
However, conventionally, a method for producing a DLC film of this segment form is a segment form by placing a wire mesh of tungsten wires on the base material at a slight interval and masking it in a lattice shape when forming the DLC film. This was a method of forming a DLC film.

JP 2003-147525 A JP 2007-83726 A

  In the above method, since the DLC adheres to the wire mesh used as a mask, the size of the mask changes with the number of times, and the wire mesh needs to be replaced about 10 times. Above all, the mask is placed on the substrate with a slight gap, and it is difficult to control the segment shape with high accuracy. If a segment-shaped film is formed on a cylindrical surface such as a roll, the control of the accuracy becomes more difficult. In particular, when using a wire mesh as a mask, it was difficult to install the wire mesh uniformly on the shaft. Even if the same film formation method as that for the DLC film is applied to the film formation of other inorganic materials, the same problem occurs.

  Accordingly, the present invention provides a method for producing a segment-shaped inorganic material film or a member having the same that can easily and accurately produce a segment-shaped inorganic material film on a substrate.

The present invention relates to the following.
1. (A) The base material surface has a pattern shape corresponding to the segment form, and the side surface of the convex pattern that can be removed is above the side surface of the projection part with respect to the end part where the projection part contacts the base material. Forming a convex pattern in a position such that at least a part of the edge covers the edge ,
(B) A ratio of the height of the protrusion / the thickness of the inorganic material film by plasma CVD of a diamond-like carbon (DLC) or inorganic material film on the surface of the substrate on which the removable convex pattern is formed. In the opening direction between the inorganic material films in the segment form by the step of forming to be 1 / 1.2 to 1/10 and the step of removing the convex pattern to which (C) DLC or the inorganic material is attached The manufacturing method of the member which has the inorganic material film | membrane of the segment form characterized by the wide recessed part being formed toward the surface .
2 . The manufacturing method of the member which has the inorganic material film | membrane of the segment form of claim | item 1 whose cross-sectional shape of a recessed part is trapezoid.
3 . (A) The base material surface has a pattern shape corresponding to the segment form, and the side surface of the convex pattern that can be removed is above the side surface of the projection part with respect to the end part where the projection part contacts the base material. Forming a convex pattern in a position such that at least a part of the edge covers the edge ,
(B) A ratio of the height of the protrusion / the thickness of the inorganic material film by plasma CVD of a diamond-like carbon (DLC) or inorganic material film on the surface of the substrate on which the removable convex pattern is formed. In the opening direction between the inorganic material films in the segment form by the step of forming to be 1 / 1.2 to 1/10 and the step of removing the convex pattern to which (C) DLC or the inorganic material is attached A method for producing an inorganic material film in the form of a segment, characterized in that a wide concave portion is formed .
4). Item 4. The method for producing a segment-shaped inorganic material film according to Item 3, wherein the recess has a trapezoidal cross-sectional shape.

According to the method for manufacturing a member having a segment-shaped inorganic material film or the method for manufacturing a segment-shaped inorganic material film according to the present invention, the segment-shaped inorganic material can be manufactured at low cost with high accuracy without using an expensive tungsten wire wire mesh. A material film can be formed on the substrate. In addition, according to the present invention, it is easy to form a highly accurate segmented film on a cylindrical surface such as a roll.
Furthermore, the inorganic material film is hardly peeled off by having the wide concave portion.

The substrate used in the present invention is not particularly limited, and examples thereof include aluminum, magnesium, alloys thereof, metals such as steel, plastics, rubber, ceramics, and composite materials thereof. sell.
Specific uses for forming the member or inorganic material film include bearings, scissors, blades, guide rails, sliding materials, resin glass, and the like.

The inorganic material film can be formed of a carbon thin film similar to diamond, a so-called diamond-like carbon (hereinafter referred to as DLC) thin film. The DLC thin film is particularly preferable because it is excellent in durability and chemical resistance.
Furthermore, the inorganic material film can be formed of an inorganic material such as an inorganic compound such as Al ₂ O ₃ or SiO ₂ .
The thickness of the inorganic material film is preferably 1 nm or more. If the inorganic material film is too thin, the durability tends to decrease. Moreover, since it is not economical when it is too thick, it is preferable that it is 200 micrometers or less.

  The shape of the segment in the present invention is not particularly limited and is appropriately determined depending on the purpose. (Positive) hexagons, (Positive) octagons, (Positive) dodecagons, (Positive) dodecagons and other (Positive) n-gons (n is an integer greater than or equal to 3), circles, ellipses, stars There are geometric figures such as molds, and these may be combined as appropriate. These units can be repeated alone or in combination of two or more.

  The size of one segment is appropriately determined, but is selected from a rectangle or a circle having one side or outer diameter of preferably 0.5 μm to 5 mm, more preferably 1 μm to 3 mm, or an area corresponding to these. The interval between adjacent segments is preferably 0.05 μm to 2 mm, and more preferably 0.1 μm to 1 mm. If one side of the size of one segment or the outer diameter is too small, the area of the inorganic material film becomes small and the mechanical strength tends to decrease. If it is too large, a large strain applied to the film accompanying the deformation of the substrate. It tends to be difficult to avoid. Also, if the interval between adjacent segments is too narrow, the gap (groove) into which the wear powder can be taken tends to be narrow, and the effect of suppressing abrasive wear tends to be reduced. Since the area is small, the mechanical strength tends to decrease.

An example of the present invention will be described with reference to the drawings.
FIG. 1 is a partial perspective view showing an example of a member having an inorganic material film in a segment form of the present invention. FIG. 2 is a cross-sectional view taken along the line AA in FIG. FIG. 2A shows a case where the side surface of the recess is planar, while FIG. 2B shows a case where the side surface of the recess has gentle irregularities. The member 1 having the segment form of the inorganic material film has the inorganic material film 3 laminated on the base material 2, and the inorganic material film 3 is formed with the concave portion 4, whereby the inorganic material film 3 is formed into the segment form. It is divided into In this example, the base material 2 is exposed at the bottom of the recess 4.
In this example, the inorganic material film 3 has a square shape as a geometric figure, and a recess 4 for dividing the inorganic material film 3 into a segment shape is formed in a groove shape around the square.
Between the base material 2 and the inorganic material film 3, an intermediate layer (not shown) may be laminated for the purpose of improving the adhesiveness of the inorganic material film 3 or the like. Or although the recessed part 4 inclines so that the side surface may spread toward the opening direction, it is not necessarily the case. Moreover, it does not necessarily have to spread uniformly with the gradient α as shown in the drawing. The concave portion may have a portion whose width is narrowed in the opening direction, but it is better that there is no such portion, and the concave portion is not narrowed in the opening direction and spreads as a whole. preferable. Such an inorganic material film can reduce friction or resistance, and is effective in effectively preventing the peeling.
The size of the segment is determined on the outermost side in the surface direction of the inorganic material film, and the interval is determined based on the size. That is, when the concave portion is not narrowed toward the opening direction but is expanded as a whole, the size and interval of the inorganic material film are determined by the bottom surface.

によってαを決定する。
αは、角度で３０度以上９０度未満が好ましく、３０度以上８０度以下がより好ましく、３０度以上６０度以下が特に好ましい。 The side surface of the recess is not necessarily a flat surface. In this case, as shown in FIG. 2 (b), the gradient α is such that the height h of the concave portion (that is, the thickness of the inorganic material film) and the width s (horizontal direction) of the side surface of the concave portion. In the width direction of the side surface of the recess)

Determines α.
α is preferably 30 ° or more and less than 90 °, more preferably 30 ° or more and 80 ° or less, and particularly preferably 30 ° or more and 60 ° or less.

The method for producing an inorganic material film in the present invention includes a step of forming an inorganic material film on a surface of a base material so that a certain shape is drawn by a recess that divides the inorganic material film into segments.
In this step, (A) forming a removable convex pattern on the surface of the substrate,
(B) including a step of forming an inorganic material film on the surface of a substrate on which a removable convex pattern is formed, and (C) a step of removing the convex pattern to which the inorganic material film is attached. .

For the step (A) of forming a removable convex pattern on the surface of the substrate, a method of forming a resist pattern using a photolithographic method can be used.
This method (Method a)
(A-1) forming a photosensitive resist layer on the substrate;
(A-2) a step of exposing the photosensitive resist layer through a mask corresponding to the conductor layer pattern, and (a-3) a step of developing the exposed photosensitive resist layer.

The step (A) of forming a removable convex pattern on the surface of the substrate can be performed by a method using laser light. This method (method b) is
(B-1) forming a photosensitive resist layer on the substrate;
(B-2) including a step of irradiating the photosensitive resist layer with a laser beam without masking a portion corresponding to the conductor layer pattern; and (b-3) a step of developing the photosensitive resist layer after the laser beam irradiation. .

In the above, the removable convex pattern corresponds to the concave pattern dividing the inorganic material film into segments.
Further, as the photosensitive resist, a well-known negative resist (a portion irradiated with light is cured) can be used. At this time, a negative mask (light passes through a portion corresponding to the concave portion) is also used as the mask. Further, a positive resist can be used as the photosensitive resist. Corresponding to these methods, the light irradiation part in the method a and method b is appropriately determined.

  As a specific method, by laminating a dry film resist (photosensitive resin layer) on a substrate, attaching a mask and exposing it, the portion that remains as a convex pattern is set in a cured state and the unnecessary part is developed. It can be formed by developing and removing unnecessary portions. In addition, the convex pattern is not necessary in the cured state by applying a liquid resist to the substrate, drying the solvent or pre-curing, and then attaching the mask and exposing to expose the portion remaining as the convex pattern. It can also be formed by making the part developable and developing and removing the unnecessary part. The liquid resist can be applied by spraying, dispenser, dipping, roll, spin coating or the like.

In the above, after laminating a dry film resist or applying a liquid resist, it is also possible to employ a method of directly exposing without using a mask with a laser beam or the like instead of exposing through a mask. If the patterning can be performed by irradiating the photocurable resin with active energy rays with or without a mask, the mode is not limited.
When the size of the substrate is large, a method using a dry film resist is preferable from the viewpoint of productivity. When the substrate is a plating drum or the like, a mask is formed after laminating the dry film resist or applying a liquid resist. A method of directly exposing with a laser beam or the like without intervention is preferable.

  In the above, it can carry out also by the method of using a thermosetting resin instead of a photosensitive resist, and removing the unnecessary part of a thermosetting resin by irradiation of a laser beam.

  Although a resist pattern (convex pattern) can be formed by using a printing method, in this case, various methods can be used as a resist pattern printing method. For example, screen printing, letterpress printing, letterpress offset printing, letterpress reversal offset printing, intaglio printing, letterpress printing, ink jet printing, flexographic printing, and the like can be used. As the resist, a photocurable or thermosetting resin can be used. After printing, the resist is cured by light irradiation or heat.

An example of a method for producing a segment-shaped inorganic material film or a member having the same in the present invention will be described with reference to the drawings.
FIG. 3 is a cross-sectional view showing an example of a process showing a method for manufacturing a segment-shaped inorganic material film or a member having the same.

  A photosensitive resist layer (photosensitive resin layer) 5 is formed on the substrate 2 (FIG. 3A). The photosensitive resist layer 5 is patterned by applying a photolithographic method to the photosensitive resist layer (photosensitive resin layer) 5 of the laminate (FIG. 3B). Patterning is performed by placing a photomask on which a pattern is formed on the photosensitive resist layer 5, exposing it, developing it, removing unnecessary portions of the photosensitive resist layer 5, and leaving protrusions 6. Done. The shape of the protrusion 6 and the convex pattern formed therefrom are considered to correspond to the concave 4 on the substrate 2 and the pattern.

At this time, in the cross-sectional shape of the protruding portion 6, the side surface is perpendicular to the base material, or at least above the side surface of the protruding portion 6 with respect to the end portion where the protruding portion 6 contacts the base material 2. It is preferable to be in a position where a portion covers the end. In terms of the width of the protrusion 6, the maximum value d ₁ of the convex pattern width is preferably equal to or larger than the width d ₀ in contact with the convex pattern and the substrate 2. This is because the concave width of the formed inorganic material film having good adhesion is determined by d ₁ . Here, as a method for making the maximum value d ₁ of the width of the protrusion 6 equal to or larger than the width d ₀ contacting the protrusion 6 and the substrate 2 in the cross-sectional shape of the protrusion 6, it is possible to overshoot during the development of the protrusion 6. A resist having a characteristic of developing or having an undercut shape may be used. d ₁ is preferably is realized at the top of the convex portion.
The shape of the protrusions 6 that form the pattern of removable protrusions is associated with the shape of the recesses. However, for ease of fabrication, the width of the protrusions is the above-mentioned d _{1 and} the width d of the bottom of the recesses. It is preferable to design so as to correspond to ′, and the height of the protrusion is preferably 1.2 to 10 times the desired thickness of the inorganic material film.

The step (B) of forming the inorganic material film on the surface of the substrate on which the removable convex pattern is formed will be described.
An inorganic material film 7 is formed on the surface of the substrate 2 having a convex pattern made up of the protrusions 6 (FIG. 3C).

  As a method for forming a DLC thin film as an inorganic material film, a physical vapor deposition method such as a vacuum vapor deposition method, a sputtering method, an ion plating method, an arc discharge method, an ionization vapor deposition method, or a chemical vapor deposition method such as a plasma CVD method is used. A dry CVD method such as the above can be employed, but a plasma CVD method using a high frequency or pulse discharge in which the film formation temperature can be controlled from room temperature is particularly preferable.

  In order to form the DLC thin film by the plasma CVD method, a hydrocarbon-based gas is preferably used as a carbon source as a raw material. For example, alkane gases such as methane, ethane, propane, butane, pentane, hexane, alkene gases such as ethylene, propylene, butene, pentene, alkadiene gases such as pentadiene, butadiene, acetylene, methylacetylene, etc. Alkyne gases, aromatic hydrocarbon gases such as benzene, toluene, xylene, indene, naphthalene and phenanthrene, cycloalkane gases such as cyclopropane and cyclohexane, cycloalkene gases such as cyclopentene and cyclohexene, methanol And alcohol gases such as ethanol, ketone gases such as acetone and methyl ethyl ketone, and aldehyde gases such as methanal and ethanal. The said gas may be used independently and may use 2 or more types together. Further, a mixture of the above-described carbon source and hydrogen gas as a raw material gas containing carbon and hydrogen as elements, and the above-described carbon source and a gas of a compound composed only of carbon and oxygen such as carbon monoxide gas and carbon dioxide gas. A mixture of a compound gas composed of only carbon and oxygen, such as a mixture, carbon monoxide gas, carbon dioxide gas, and hydrogen gas; a compound gas composed of only carbon and oxygen, such as carbon monoxide gas, carbon dioxide gas; Examples thereof include a mixture with oxygen gas or water vapor. Further, these source gases may contain a rare gas. The rare gas is a gas composed of an element belonging to Group 0 of the periodic table, and examples thereof include helium, argon, neon, and xenon. These rare gases may be used alone or in combination of two or more.

The whole of the inorganic material film may be formed of the insulating DLC thin film described above, but the adhesion of the DLC thin film to a substrate such as a metal plate is improved, and the durability of the inorganic material film is improved. In order to further improve, it is preferable to insert an intermediate layer composed of one or more components selected from Ti, Cr, W, Si, nitrides or carbides thereof, or the like, between the two.
The Si or SiC thin film has excellent adhesion to, for example, a metal such as stainless steel, and also forms SiC at the interface with the insulating DLC thin film laminated thereon to improve the adhesion of the DLC thin film. Has the effect of improving.
The intermediate layer can be formed by the dry coating method as described above.
The thickness of the intermediate layer is preferably 1 μm or less, and more preferably 0.5 μm or less in consideration of productivity. A coating of 1 μm or more is not suitable because the coating time becomes long and the internal stress of the coating film increases.

Even when the inorganic material film is formed of an inorganic material such as an inorganic compound such as Al ₂ O ₃ or SiO ₂ , a physical vapor deposition method such as a sputtering method or an ion plating method, or a chemical vapor deposition method such as plasma CVD. Can be used. For example, in the case of forming by sputtering, an oxide or nitride such as SiO ₂ or Si ₃ N ₄ can be formed by introducing Si or Al as a target and introducing oxygen, nitrogen or the like as a reactive gas. it can. In the case of using the ion plating method, Si or Al can be used as a raw material, and an electron beam can be irradiated to evaporate to form a film on the substrate. At that time, an oxide, nitride, or carbide film can be formed by introducing a reactive gas such as oxygen, nitrogen, or acetylene.
In the case of forming a film by the CVD method, the film can be formed by using a chemical gas such as a metal chloride, a metal hydride, an organometallic compound, etc. as a raw material. The CVD of silicon oxide can be performed by plasma CVD using, for example, TEOS or ozone. The CVD of silicon nitride can be performed by plasma CVD using ammonia and silane, for example.

Next, the process of removing the convex pattern to which the above-described (C) inorganic material film is attached will be described. In a state where the inorganic material film 7 is attached (see FIG. 3C), the convex pattern composed of the protrusions 6 is removed (see FIG. 3D).
For removing the resist to which the inorganic material film is attached, a commercially available resist stripping solution, inorganic, organic alkali, organic solvent, or the like can be used. In addition, if there is a dedicated stripping solution corresponding to the resist used to form the pattern, it can be used.
As a peeling method, for example, it is possible to remove the resist after it has been swelled, broken or dissolved by immersion in a chemical solution. In order to sufficiently impregnate the resist with the solution, techniques such as ultrasonic waves, heating, and stirring may be used in combination. In addition, the liquid can be applied with a shower, a jet or the like in order to promote peeling, and can be rubbed with a soft cloth or cotton swab.
Further, when the heat resistance of the inorganic material film is sufficiently high, a method of baking at a high temperature to carbonize the resist and removing it, or burning off by irradiating with a laser can be used.
As the stripping solution, for example, a 3% NaOH solution is used, and showering or dipping can be applied as the stripping method.

The inorganic material film formed on the substrate 2 and the inorganic material film formed on the side surface of the protrusion 6 are made to have different properties or characteristics. That is, the hardness of the former is greater than the latter. This is the case when the DLC film is formed by plasma CVD. In general, when an insulating film is formed, when the moving speed of the insulating material is different by, for example, an angle of 90 degrees, the properties or characteristics of the film formed as described above are different.
The distance from the side surface of the convex pattern (as a plane perpendicular to the base material) between the inorganic material film formed on the base material and the inorganic material film formed on the side surface of the convex pattern is the convex pattern. It is preferable that it does not become small toward the standing position, but becomes large as a whole.
The side surface of the convex pattern (as a surface perpendicular to the substrate) is the surface if the side surface of the convex pattern is perpendicular to the substrate, but the side surface of the convex pattern is the substrate side. In the case of covering the surface, the side surface of the convex pattern is a vertical surface rising vertically from the point ending with the substrate.
When the protrusion 6 is removed, the inorganic material film is separated at this boundary, and as a result, the side surface of the recess has an inclination angle α. The inclination angle α is preferably 30 degrees or more and less than 90 degrees, more preferably 30 degrees or more and 80 degrees or less, further preferably 30 degrees or more and 60 degrees or less, and particularly preferably 40 degrees or more and 60 degrees or less, and the DLC film is plasma-treated. In the case of manufacturing by CVD, it becomes easy to control to about 40 to 60 degrees. That is, the concave portion 4 is formed so as to become wider toward the opening direction. As a method of controlling the inclination angle α, a method of adjusting the height of the protrusion 6 is preferable. As the height of the protrusion 6 increases, the inclination angle α can be controlled more greatly.

  In the formation of the above-described inorganic material film, the surface portion of the base material without the convex pattern does not become a shadow of the resist, so that the inorganic material film on this has uniform properties. On the other hand, the formation of the inorganic material film on the side surface of the convex pattern is because the side surface of the convex pattern has an angle with respect to the film thickness direction on the substrate. As for (film), an inorganic material film having the same characteristics (for example, the same hardness) as the inorganic material film on the substrate cannot be obtained. At the contact surface of such a different inorganic material film, the boundary surface of the inorganic material film is formed with the growth of the inorganic material film, and the boundary surface is a growth surface of the inorganic material film. is there. For this reason, when removing the convex pattern consisting of the protrusions, the inorganic material film (particularly the DLC film) is easily separated at this boundary. Furthermore, since the growth of the inorganic material film is delayed on the side surface of the protrusion with respect to the film thickness direction on the substrate, the inclination angle α that becomes the boundary surface, that is, the side surface of the concave portion, Control is performed as described above.

In the present invention, the hardness of the inorganic material film formed on the substrate is preferably 10 to 40 GPa. An inorganic material film having a hardness of less than 10 GPa is soft and has low durability in repeated use. When the hardness is 40 GPa or more, when the base material is processed such as bending, the base material cannot follow the deformation of the base material, and the inorganic material film is likely to be cracked or cracked. The hardness of the inorganic material film formed on the substrate is more preferably 12 to 30 GPa.
On the other hand, the hardness of the inorganic material film formed on the side surface of the convex portion is preferably 1 to 15 GPa. The inorganic material film formed on the side surface of the convex portion must be formed so as to be at least lower than the hardness of the inorganic material film formed on the substrate. By doing so, a boundary surface is formed between the two, and a wide concave portion is formed after a step of peeling the convex pattern composed of the projection portion to which the inorganic material film adheres later. The hardness of the inorganic material film formed on the side surface of the protrusion is more preferably 1 to 10 GPa.

The hardness of the inorganic material film can be measured using a nanoindentation method. In the nanoindentation method, a regular triangular pyramid (Berkovic) indenter with a diamond tip is pressed into the surface of a thin film or material, and the hardness is obtained from the load applied to the indenter and the projected area under the indenter. As a measurement by the nanoindentation method, a device called a nanoindenter is commercially available. The hardness of the film formed on the substrate can be measured by pressing an indenter from the substrate as it is. Also, in order to measure the hardness of the film formed on the side surface of the convex part, a part of the base material is cut out and cast with resin, and an indenter is pushed into the inorganic material film formed on the side surface of the convex part from the cross section. Can be measured. Normally, in the nanoindentation method, the hardness is measured by applying a minute load of 1 to 100 mN to the indenter, but in the present invention, the value measured by applying a load of 3 mN for 10 seconds is described as the hardness value.
In this way, a segment-shaped inorganic material film or a member having the same can be produced.

FIG. 4 shows a cross-sectional view of a member having an intermediate layer between a segment-shaped inorganic material film and a substrate and a precursor thereof.
It is preferable to form the intermediate layer 8 before forming the inorganic material film 7 on the surface of the base material 2 on which the convex pattern composed of the protrusions 6 is formed (FIG. 4 (c ′)). As the intermediate layer, those described above can be used, and the formation method is also as described above. In the case where the intermediate layer 8 is formed, the base material 2 is exposed at the bottom of the recess 4 in the obtained member, and the inorganic material film 7 is formed on the intermediate layer 8 in other cases (FIG. 4). (D ′)). The intermediate layer may be formed on the surface of the substrate 2 before the convex pattern 6 is formed. Thereafter, a step of forming a segment-shaped inorganic material film on the surface as described above may be performed. In this case, the bottom of the recess may remain as the intermediate layer, but the base layer 2 may be exposed by removing the intermediate layer at the bottom of the recess by a method such as dry etching.

(Formation of convex pattern)
A resist film (Photech RY3315, 10 μm thick, manufactured by Hitachi Chemical Co., Ltd.) was bonded to a 150 mm square stainless steel plate. The bonding conditions were a roll temperature of 105 ° C., a pressure of 0.5 MPa, and a line speed of 1 m / min. Next, the line width of the light transmission part is 0.1 mm, the line pitch is 1 mm, and the bias angle is 45 ° (in the regular square, the line is arranged at an angle of 45 degrees with respect to the side of the regular square. Thus, a negative film in which a pattern was formed in a grid shape with a size of 120 mm square was left on one side of an aluminum plate. Using an ultraviolet irradiation device, ultraviolet rays were irradiated at 120 mJ / cm ² from above the aluminum plate on which the negative film was placed under a vacuum of 600 mmHg or less. Furthermore, by developing with a 1% aqueous sodium carbonate solution, a lattice pattern consisting of a protrusion resist film (protrusion; height 10 μm) having a line width of 0.1 mm, a line pitch of 1 mm, and a bias angle of 45 degrees on an aluminum plate Formed.

(Formation of DLC film)
A DLC film was formed using a PBII / D apparatus (Type III, manufactured by Kurita Seisakusho Co., Ltd.). An aluminum plate with a resist film attached thereto was put in the chamber, the inside of the chamber was evacuated, and the substrate surface was cleaned with argon gas. Next, hexamethyldisiloxane was introduced into the chamber, and an intermediate layer was formed to a thickness of 0.1 μm. Next, toluene, methane, and acetylene gas were introduced, and a DLC layer was formed on the intermediate layer so as to have a film thickness of 1 μm (corresponding to FIG. 3C).

(Concavity formation; removal of convex pattern with DLC attached)
The stainless steel substrate with the insulating layer attached was immersed in an aqueous sodium hydroxide solution (10%, 50 ° C.) and left for 8 hours with occasional rocking. The resist film forming the convex pattern and the DLC film adhering thereto have been peeled off. Since there was a part that was not easily peeled off, the entire surface was peeled off by lightly rubbing with a cloth to form a segmented DLC film. Regarding the dimensions of the DLC segment, the segment interval was 0.1 mm, the segment pitch was 1 mm, and the depth of the recess (groove) was about 1 μm, and a precise shape could be obtained. The angle of the side surface of the recess was approximately 45 °.

(Abrasion resistance evaluation)
The obtained member was subjected to a ball-on-disk test [according to JIS R 1613 (1993)]. The vertical load is 0.71 N and the test time is 5000 s. As a result, it was able to withstand up to about 12,000 revolutions.

(Formation of convex pattern)
Liquid resist (ZPN-2000, manufactured by Nippon Zeon Co., Ltd.) φ100mm, length 30
It apply | coated so that it might become thickness 6 micrometers on the titanium cylindrical surface of 0 mm. After pre-baking at 110 ° C. for 1 minute, exposure was performed using an ultraviolet irradiation device so that the line width of the light transmission portion was 0.1 mm, the line pitch was 1 mm, and the bias angle was 45 °, and heating was performed at 115 ° C. for 1 minute. Then, the pattern which consists of a resist film was formed by developing with 2.38% of tetramethylammonium hydroxide (TMAH).

(Formation of film)
DLC was formed in the same manner as in Example 1.

(Concavity formation; removal of convex pattern with film attached)
The titanium substrate to which the film was adhered was immersed in an aqueous sodium hydroxide solution (10%, 50 ° C.) and left for 2 hours while applying ultrasonic waves at 50 kHz. The resist film forming the convex pattern and the DLC film adhering thereto have been peeled off. Since there was a part that was not easily peeled off, the entire surface was peeled off by lightly rubbing with a cloth to form a segmented DLC film. Regarding the dimensions of the DLC segment, the segment interval was 0.1 mm, the segment pitch was 1 mm, and the depth of the recess (groove) was about 1 μm, and a precise shape could be obtained. The angle of the side surface of the recess was approximately 45 °.

(Abrasion resistance evaluation)
The obtained member was subjected to a ball-on-disk test in the same manner as in Example 1. As a result, like Example 1, it was able to endure up to about 12000 rotations with a vertical load of 0.71 N and a test time of 5000 s.

(Comparative Example 1)
A wire mesh having an opening portion of 1 × 1 mm was produced from a tungsten wire having a wire diameter of φ0.1 mm, and DLC was formed on an aluminum plate in the same manner as in Example 1 using this as a mask. The tungsten wire was in an electrically floating state during film formation. Initially, the DLC segment interval was 0.1 mm, but as the number of times increased, the DLC adhered to the tungsten wire, and the segment interval gradually increased. Eventually, at the 10th time, the segment interval was crossed and the tungsten wire had to be replaced.

(Comparative Example 2)
To form DLC segments on an aluminum cylindrical surface with a diameter of 100 mm and a length of 300 mm, a tungsten wire with a diameter of 0.1 mm is used to produce a cylindrical wire mesh with an opening of 1 × 1 mm and a diameter of about 100 mm. Tried to install. However, in order to make the tungsten wire electrically floating, it is necessary to insert spacers having a thickness of at least 0.1 mm and a width of 1 mm at both ends and the center of the cylindrical surface. It has been found that restrictions occur. Even if a spacer is used, it is extremely difficult to place a tungsten wire mask on the aluminum cylindrical surface with a uniform gap.

The partial perspective view which shows an example of the member which has the inorganic material film | membrane of the segment form of this invention. AA sectional drawing of FIG. Sectional drawing which shows an example of the process which shows the manufacturing method of the inorganic material film | membrane of a segment form, or a member which has it. Sectional drawing of the member which has an intermediate | middle layer between the inorganic material film | membrane of a segment form, and a base material, and its precursor.

Explanation of symbols

1: Member having an inorganic material film in segment form 2: Base material 3: Inorganic material film 4: Recessed part 5: Photosensitive resist layer (photosensitive resin layer)
6: Projection 7: DLC film 8: Intermediate layer

Claims (4)

(A) The base material surface has a pattern shape corresponding to the segment form, and the side surface of the convex pattern that can be removed is above the side surface of the projection part with respect to the end part where the projection part contacts the base material. Forming a convex pattern in a position such that at least a part of the edge covers the edge,
(B) A ratio of the height of the protrusions / the thickness of the inorganic material film by plasma CVD with a film of diamond-like carbon (DLC) or an inorganic material on the surface of the substrate on which a removable convex pattern is formed. In the segment form formed of DLC or inorganic material by the step of forming 1.2 / 1 to 10/1 and (C) the step of removing the convex pattern to which DLC or inorganic material is adhered A method for producing a member having a segment-shaped inorganic material film, wherein a wide concave portion is formed in the opening direction between the inorganic material films.   The method for producing a member having a segment-shaped inorganic material film according to claim 1, wherein the recess has a trapezoidal cross-sectional shape. (A) The base material surface has a pattern shape corresponding to the segment form, and the side surface of the convex pattern that can be removed is above the side surface of the projection part with respect to the end part where the projection part contacts the base material. Forming a convex pattern in a position such that at least a part of the edge covers the edge,
(B) A ratio of the height of the protrusions / the thickness of the inorganic material film by plasma CVD with a film of diamond-like carbon (DLC) or an inorganic material on the surface of the substrate on which a removable convex pattern is formed. In the segment form formed of DLC or inorganic material by the step of forming 1.2 / 1 to 10/1 and (C) the step of removing the convex pattern to which DLC or inorganic material is adhered A method for producing a segment-shaped inorganic material film, characterized in that a wide concave portion is formed in the opening direction between the inorganic material films.   The method for producing a segment-shaped inorganic material film according to claim 3, wherein the cross-sectional shape of the recess is a trapezoid.

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