JP2010242227A - Member for loom and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To achieve the long life of guide components of fiber (yarn) arranged as a subsidiary member of various looms and to reduce a cost of operation of these components. <P>SOLUTION: A stainless steel product having a component composition of [amount of (Cr+Mo) in steel-amount of (Ni+Cu) in steel]≥7 mass% is used as a steel base material. The stainless steel product is treated by plasma etching and activated. A hydrocarbon-based gas is introduced in the atmosphere of the treatment, an amorphous hydrocarbon solid fine particle composed of carbon and hydrogen as main components is vapor-deposited under condition in which the steel base material is set in a negative potential to form a DLC thin film having the thickness of 1.5-10 μm. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a member used for guiding a yarn, such as a kite, heald, sword, buckleet, and the like used in a loom for weaving various fibers, and a method for manufacturing the member.

  Textile machines for weaving natural fibers such as cotton and wool, synthetic fibers such as polyester and nylon, new material fibers such as carbon fibers and high-performance fibers, such as looms and shaping machines, A member called “Osa” is used.

  The “osa” which is one of the members for the loom is a part used for adjusting the texture by aligning the warp of the woven fabric or pressing the weft. This “osa” is constituted by arranging a large number of metal thin plates in parallel at intervals of about 0.5 to 1 mm and supporting the periphery thereof by a frame body called a rim. As for such “osa”, stainless steel has generally been used. However, with regard to “Osa” in recent years, a new material fiber that is made by gluing raw yarns with a diameter of 1 to 2 μm, called filaments, is born, and such fibers run at high speed. Therefore, the following performance is required.

(1) The surface of “osa” is smooth, has little contact resistance with the yarn running at high speed, and has excellent wear resistance.
(2) When the raw yarn to be used is one containing ultrafine particles such as CuO or TiO _{2 in} order to improve heat retention using far infrared rays or to exhibit bactericidal properties using ultraviolet rays, It has good wear resistance against the raw yarn,
(3) The paste impregnated in the raw yarn is difficult to adhere and can be easily removed even if the paste adheres;
(4) Even if washing with water, acid, or alkaline aqueous solution performed to remove glue attached to the surface of “OSA” is performed, a healthy state can always be maintained.

  Conventionally, various stainless steels have been adopted as “osa” base materials having the performances (1) to (4) above, and various surface treatments have been proposed on the surface thereof.

For example, the typical representative “osa” is generally one in which the surface of the substrate is plated with hard chrome, but thereafter, as seen in Patent Documents 1 and 2, Have been proposed in which a hard and smooth Cr ₂ O ₃ thin film is formed on the surface. Furthermore, in recent years, “osa” in which an amorphous “DLC” thin film mainly composed of carbon and hydrogen is coated on the surface of the base material has been developed, and it is smooth and hard and has low frictional resistance with the yarn. It is used as a member that is not corroded by acid or alkaline aqueous solution.

  However, since this DLC thin film had poor adhesion, it was not directly formed on the surface of the stainless steel substrate. That is, generally, a metal film (undercoat) made of Cr, Ti, Si, SiC or the like is first formed on the surface of the stainless steel substrate by a PVD method or the like (Patent Documents 3 to 3). 5).

JP-A 61-245346 Japanese Patent Laid-Open No. 11-029876 JP-A-6-060404 JP-A-9-105051 Japanese Patent Laid-Open No. 10-037043

Each of the above-described conventional techniques relating to the production of “OSA”, which is one of the parts for a loom, has the following problems to be solved. that is,
(1) A DLC thin film that exhibits excellent adhesion and wear resistance over a long period of time cannot be provided at low cost.
(2) Workability and productivity because the DLC thin film is indirectly formed on the surface of “Osa” substrate by forming various metal and carbide undercoats by electroplating and PVD methods. Is bad.
(3) Corrosion resistance and durability of the DLC thin film itself are inferior, and the quality remains uneasy.

In addition, the undercoat thin film requires a long processing time, and in order to coat the Cr film by electroplating, a plating solution containing a large amount of harmful hexavalent chromium (usually, CrO ₃ 250 g / L, H ₂ SO ₄ 2.5 g / L) is used, which causes environmental pollution and is not a preferred method.

As a result of researches to solve the above-described problems of the prior art, the inventors have obtained the following knowledge that is linked to effective solutions.
(1) If it is decided to directly form a DLC thin film with excellent adhesion on the surface of a metal “osa” base material, it is possible to omit the undercoat, which was essential in the prior art. As a result, production costs can be greatly reduced.
(2) In order to directly apply the DLC thin film to the surface of the base material for “OSA”, select the type of base material, that is, the steel type, and set its chemical composition and composition within a predetermined range. Is essential.
(3) In order to directly form the DLC thin film on the surface of the “osa” base material made of the selected steel type, it is effective to perform a pretreatment. In this pretreatment, a negative potential is applied to the base material in a vacuum vessel, and an inert gas such as Ar and He is ionized in a plasma state, and the ions collide with the surface of the base material. It is effective to perform a treatment for removing the oxide film on the surface of the substrate.
(4) Along with the above treatment, a small atomistic dent is added to the collision surface to activate not only the crystal plane but also the crystal grain boundary, and then introduce hydrocarbon gas into the same vacuum vessel. It is preferable to generate a DLC thin film.

  That is, the present invention provides a member for a loom, characterized in that a surface of a steel substrate that has been polished and activated is directly coated with a deposited film of an amorphous carbon hydrogen solid, Let it be said problem-solving means.

  In the present invention, the surface of the steel substrate is polished to a smooth surface, and then the steel substrate is set to a negative potential in an inert gas such as Ar or He. The substrate surface is activated by performing plasma etching treatment, and then the substrate is set to a negative potential in the same atmosphere, then a hydrocarbon gas is supplied, and a high-frequency high-voltage pulse is applied. Is applied to deposit a layer of amorphous carbon hydrogen solid particles mainly composed of carbon and hydrogen on the surface of the base material in a vapor phase (hereinafter referred to as this film). Is simply referred to as a “DLC thin film”).

In the present invention,
(1) The steel base material is a stainless steel in which the sum of the mass contents of Cr and Mo is 7 mass% or more than the sum of the mass contents of Ni and Cu contained in the same base material. Using
(2) The steel substrate is subjected to plasma etching in an inert gas having a polished surface with Ra ≦ 0.5 μm, Rz ≦ 1.5 μm, and pressure: 0.1 to 1.0 Pa. Having an activated surface,
(3) The carbon hydrogen solid deposit film has a thickness in the range of 1.5 to 10 μm,
(4) The carbon hydrogen solid deposit film has a hydrogen content of 13 to 22 atomic% in the film, the balance is made of carbon, and the hardness is in the range of Hv: 1000 to 2700,
Is a more preferable solution.

According to the present invention, the following effects can be expected.
(1) Since the DLC thin film is directly coated on the surface of the base material to be “osa” or the like, an undercoat made of Cr, Ti, Si, WC, SiC, or the like is not required. This eliminates the need for various devices, processing time, costs, materials, and the like necessary for undercoat construction, and reduces processing time. In addition, productivity is greatly improved, and in addition to the effect of reducing production costs, it also becomes a resource saving measure.
(2) Since the undercoat can be omitted, the electroplating that has been conventionally performed for this treatment, especially chromium plating (a hexavalent chromium aqueous solution (CrO ₃ ) that is severely restricted as an environmental pollution component) Used), the safety of the entire work can be improved, and the work environment can be improved.
(3) The DLC thin film used in the present invention has a high Hv of 1000 to 2700, a small contact resistance value with a fiber, excellent wear resistance, and good adhesion, so that it is resistant to strong bending deformation. Shows sufficient durability.
(4) The DLC thin film used in the present invention is composed of vapor-deposited fine particles having a hydrogen content of 13 to 22 atomic% and the balance being carbon, so that the DLC thin film has flexibility and the “osa” in use is deformed. Even in this case, it can be followed sufficiently, and it is not eroded by an acid or alkaline aqueous solution, and the initial performance can be maintained for a long period of time.

FIG. 5 is a process diagram for coating a DLC thin film on the surface of “osa”. It is the cross-sectional schematic diagram of the surface roughness of the base material for "osa", and the DLC thin film formed on it, When (a) is a DLC thin film with a film thickness thinner than Rz, (b) is from Rz This is a case where a thick DLC thin film is formed. It is a schematic diagram of the plasma CVD apparatus for coating-forming a DLC thin film on the surface of a base material. It is the typical evaluation sample photograph from which the peeling state of a scratch flaw and thin film for evaluating the adhesiveness of a DLC thin film differs. Evaluation 1 is an example of a DLC thin film with the best adhesion, and Evaluation 4 is an example of a thin film with the lowest adhesion. FIG. 3 is a schematic view of an “osa” base material wear resistance test apparatus.

The following description will be given exclusively with the example of a loom as a member for a loom, but the present invention is not limited only to that "was".
FIG. 1 is a process diagram of the method of the present invention in which a DLC thin film is formed directly on the surface of a base material which is the basis of the thickness “osa”. The configuration of the present invention will be described below with reference to this figure.

(1) Selection of material for “Osa” base material;
In the present invention, first, it is possible to select a base material suitable for directly forming a DLC thin film without interposing an intermediate layer such as a so-called undercoat on the surface of the base material to be the “OSA” body. is important. That is, in order to directly coat and form an amorphous DLC thin film mainly composed of carbon and hydrogen on the surface of a metal substrate with high adhesion, the chemical components, composition, and characteristics of the metal substrate. It is important to consider such things.

  In the present invention, when considering the use environment of the “osa” as an accessory of a loom, it was considered that a steel material is effective as a base material. Therefore, a DLC thin film was directly coated on many steel types, and the adhesion of the thin film was examined. As a result, it was found that the following relationship was established between the chemical composition of the steel (base material) and the adhesion of the DLC thin film.

(A) Metal component exhibiting good adhesion: Cr, Mo, Nb, Ta, Si, W (C, C ₂₃ C ₆ )
(B) Metal components that inhibit adhesion: Ni, Cu
(C) Metal and non-metallic components with low content and low impact: Mn, P, S
Note that (a) C and C ₂₃ C ₆ indicated as metal components exhibiting good adhesion are not metal components, but are included in (a) for convenience because they are often non-metallic components contained in steel. It was.

  Therefore, even if it is carbon steel, since the general structural steel (SS400) does not contain components such as Cr and Mo, the DLC thin film directly coated on the surface of this steel has poor adhesion. On the other hand, high carbon steel (SC480, SK140), etc. can form a DLC thin film with high adhesion compared to the former SS400 steel, but it is difficult to process into a thin plate like “Osa”. Yes, it was not the right material.

  From the above results, it is desirable that the base material for “osa” be made of steel. Considering mechanical properties, workability, economy, difficulty of acquisition, etc., the use of stainless steel is desirable. Is considered the most appropriate. However, since stainless steel contains Cr and Mo as adhesion improving components, and often contains Ni and Cu that inhibit adhesion, it has been found that some component adjustment is necessary. Therefore, in the present invention, in determining the base steel type and the component composition, the following component composition that has been clarified from the experimental results shown in Example 1 and the like is used.

  That is, in this invention, the sum total of the component which improves the adhesiveness of DLC thin films, such as Cr and Mo, is contained extra by the ratio of 7 mass% or more rather than the sum of Ni and Cu which are adhesiveness inhibiting components. Stainless steel is used as the preferred steel grade. That is, the effective amount for improving the film adhesion is 7 mass% or more. In addition, the calculation described below is based on chemical components described in Japanese Industrial Standard, and when a certain component range is shown, an intermediate value thereof is used.

(2) Calculation formula for selecting compatible steel types;
Active ingredient amount = (Cr + Mo) amount in steel− (Ni + Cu) amount in steel ≧ 7 mass%
Table 1 shows the results of determining the effective component amounts of various stainless steel chemical component amounts using the above-described effective component amount calculation formula. As is clear from this result, even if it is SUS310 steel containing a large amount of Cr, it becomes a non-conforming steel type when the amount of Ni is large, and SUS410 steel not containing Ni becomes a conforming steel type. It has been found that is not a consistent steel grade.

  As for the above stainless steel, attention is focused only on Cr, Mo, Ni, and Cu as influence components affecting the adhesion of the DLC thin film to the “osa” base material. The effects of various metal carbides including metal elements such as Ta, Si, and W are also conceivable, but these components are not included or even if included, these components (metal) Elements and carbides) were excluded from the calculation.

(3) Production of “OSA” and its surface polishing;
The “osa” cut from the selected stainless steel substrate is then polished on its surface. The “osa” dimension is a thin plate having a width of 3 to 10 mm, a length of 80 to 120 mm, and a thickness of about 0.1 to 0.7 mm, although there are some differences depending on the purpose. It is important to polish the thin steel plate by barrel polishing, automatic buffing, etc. to polish not only the surface (both sides) of the steel plate but also the edges to eliminate sharp edges. Moreover, you may finish to a mirror surface using chemical polishing or electrolytic polishing as needed.

In the present invention, it is preferable that the surface of the “osa” substrate is polished and finished to have the following roughness.
Arithmetic average roughness Ra: 0.5 μm or less Ten-point average roughness Rz: 1.5 μm or less

  The reason why the surface roughness values (Ra, Rz) of the substrate are regulated as described above is as follows. That is, when the polished surface of the base material is measured with a stylus type surface roughness meter, Ra value, Rz value, Ry value, etc. can be easily measured. The polished surface on the surface of the substrate always had a small Ra value and a large Rz value. In particular, within the surface roughness range recommended by the present invention, the Rz value often reached 4 to 7 times the Ra value.

  When a DLC thin film is formed on the surface of a substrate having a polished surface with a high Rz value, a state as shown in FIG. 2 is obtained. That is, the DLC film formed on the surface of the “Osa” substrate is a very thin film. Therefore, the DLC film 24 having the convex portion 23 that substantially determines the Rz value on the polished surface cannot obtain a substantial effective film thickness even if the convex portion 25 is exposed or not exposed. It will be. For this reason, the convex part exposed from the DLC film may cause the raw yarn to be cut or the fibers to be damaged.In addition, in the DLC film having a small effective film thickness, even if the DLC film is slightly worn during operation, Only the convex portions are exposed, which causes damage to the yarn and the fibers. In FIG. 2, 21 is a base material, and 22 is a roughness indicated by Ra.

(4) Activation of the substrate surface (plasma etching treatment);
In the present invention, a plasma etching process is performed as a pretreatment for activation so that the DLC thin film can be directly coated on the surface of the polished “osa” substrate. There are many techniques for performing a plasma etching process on a substrate for “sa”, but in the present invention, the plasma etching process and the DLC thin film can be performed using the same apparatus. Use of a voltage pulse superposition type plasma CVD method (hereinafter simply referred to as “plasma CVD method”) is preferable.

  FIG. 3 is a schematic diagram of a plasma CVD apparatus capable of performing plasma etching and forming a DLC thin film. The plasma CVD apparatus includes a grounded reaction vessel 31, a high-voltage pulse generating power source 34 for applying a high-voltage pulse in the reaction vessel, and a periphery of an object to be processed (“Osa” substrate) 32. Is provided with a plasma generating power source 35 for generating Ar gas plasma, hydrocarbon gas plasma, and the like, and for applying both a high voltage pulse and a high frequency voltage to the conductor 33 and the object to be processed simultaneously. A superimposing device 36 is interposed between the high voltage pulse generating power source 34 and the plasma generating power source 35. The conductor and the object to be processed are connected to the superimposing device via the high voltage introduction unit 39.

  This plasma CVD apparatus includes a gas supply device (not shown) and a reaction vessel for introducing an inert gas such as Ar or He for plasma etching and various hydrocarbon gases for forming a DLC thin film into the reaction vessel. A vacuum pump (not shown) for evacuation is connected to the reaction vessel via valves 37a and 37b, respectively.

  Next, a method for activating the surface of the object to be processed by plasma etching using this plasma CVD apparatus and its mechanism of operation will be described. First, an object to be treated is placed at a predetermined position in a reaction vessel, a vacuum apparatus is operated, air in the reaction vessel is discharged and deaerated, and then Ar gas is introduced into the reaction vessel by a gas supply device. The pressure is adjusted to 0.1 to 1.0 Pa.

Next, when high frequency power is applied from the plasma generating power source 35 to the object to be processed, the Ar gas molecules emit electrons and generate a large amount of Ar ⁺ ions. Since the reaction vessel is in an electrically neutral state by the ground wire 38, the object to be processed has a relatively negative potential, and positively charged Ar ⁺ ions are applied to the surface of the object to be processed having a negative potential. It will impact. This phenomenon is called ion bombardment. According to the knowledge of the inventors, a metal oxide film (mainly Cr oxide film) that causes a decrease in adhesion of the DLC film at the ion collision portion on the surface of the object to be processed. Are completely removed on an atomic scale to expose the activated metal surface. More specifically, the diameter of Ar molecules used for plasma etching is about 3.8 × 10 ⁻¹⁰ m, and the diameter is further reduced with Ar ⁺ ions in a state where electrons are emitted. In addition, the surface of the workpiece to which these ions collide as a group has an atomic scale, and the exposed metal surface as well as the oxide film is continuously subjected to a microscopic etching action. Therefore, the surface of the “osa” substrate is completely activated. In particular, in the present invention, in order to form directly on the surface of the DLC thin film substrate, a relatively large amount of Cr is contained in the “osa” substrate. This Cr has a chemical affinity with oxygen. The plasma etching process is an extremely important process because it has a function of easily forming a Cr oxide film even when exposed to air and hindering the adhesion of the DLC thin film.

In particular, in the activation treatment of the substrate surface by this plasma etching, the protruding portion existing on the substrate surface, specifically, the tip portion having a roughness indicated by Rz or Ry tends to be etched strongly. In this sense, it is effective to eliminate the protrusions on the surface of the base material or to reduce the protrusions so that they do not disappear. In experiments conducted by the inventors using a SUS410 steel base material, the surface roughness of the base material before and after the plasma etching treatment is as shown below. The effect is recognized also about sex. The etching time in this experiment is 20 minutes.
Before plasma etching treatment Ra: 0.09 μm, Rz: 0.28 μm
After plasma etching treatment Ra: 0.09 μm, Rz: 0.16 μm

Here, an example in which Ar is used as the plasma etching gas has been described, but it is possible to apply He or N ₂ gas or other low-mass hydrocarbon gas such as CH ₄ or C ₂ H _4. . In particular, when a hydrocarbon-based gas is used, a carbon component is injected into the surface of the “osa” base material, which shows the same function as the undercoat, and adheres to the DLC thin film. It is effective for improving the performance.

(5) DLC thin film coating formation;
Next, after the plasma etching process is completed, a hydrocarbon gas is introduced into the container while the object to be processed is still installed in the reaction container. Next, when a high voltage pulse (negative high voltage pulse) from the high voltage pulse generator is applied to the object to be processed, a part of the introduced hydrocarbon gas is turned into plasma, and the positive ions therein are charged. As a result, the DLC thin film consisting of an amorphous solid mainly composed of carbon and hydrogen is vapor-deposited on the surface of the object to be treated. Will be.

The inventors believe that the amorphous DLC thin film formed on the surface of the object to be processed using the high-voltage pulse generator is formed through the following processes (a) to (d). .
(A) ionization of the introduced hydrocarbon gas (neutral particles called radicals also exist),
(B) Ions and radicals changed from the hydrocarbon-based gas collide impactively with the surface of the carrier body 42 to which a negative voltage is applied,
(C) C—H having a low binding energy is cut by the energy at the time of collision, and then activated C and H are polymerized by repeating the polymerization reaction to form an amorphous state mainly composed of carbon and hydrogen. Vapor deposition of carbon hydrogen solids of
(D) When the reaction (c) occurs, a DLC thin film composed of a deposited layer of amorphous carbon hydrogen solid particles is formed on the surface of the object to be processed.

In the apparatus used in the present invention, either the plasma etching process for activation or the DLC thin film forming process can be performed by changing the output of the high voltage pulse generating power source. For example, the output is as follows.
(A) In the case of processing for forming only a DLC thin film: several hundred V to several KV
(B) When performing plasma etching treatment intensively: several hundred V to several tens KV
In addition, the generation of the high voltage pulse is performed under the following conditions.
(C) Pulse width: 1 μsec to 10 msec
(D) Number of pulses: 1 to a plurality of repetitions In addition, the output frequency of the high frequency power in the plasma generation power source can be changed in the range of several tens KHz to several GHz.

Further, as a kind of organic gas for film formation used for coating the DLC thin film, a gas composed of the following hydrocarbon compounds mainly containing carbon and hydrogen is preferably used.
(I) Gas phase state at room temperature (18 ° C.) CH ₄ , CH ₂ CH ₂ , C ₂ H ₂ , CH ₃ CH ₂ CH ₃ , CH ₃ CH ₂ CH ₂ CH ₃
(B) Liquid phase at normal temperature C ₆ H ₅ CH ₃ , C ₆ H ₅ CH ₂ CH, C ₆ H ₄ (CH ₃ ) ₂ , CH ₃ (CH ₂ ) ₄ CH ₃ , C ₆ H ₁₂ ,
C ₆ H ₄ Cl

  The above-mentioned compound in the vapor phase at normal temperature is introduced into the reaction vessel as it is, and in the liquid phase, it is gasified by heating, and the gas (vapor) is supplied into the reaction vessel. To form a DLC thin film.

  As a characteristic of the DLC thin film used in the present invention, it is necessary to combine moderate flexibility and wear resistance. In this regard, the inventors conducted various experiments paying attention to the ratio of carbon and hydrogen, which are constituents of the thin film. As a result, it was found that a desirable DLC thin film is effective when the hydrogen content is 13 to 22 atomic% and the balance is composed of a carbon component. In addition, in order to control the ratio of hydrogen and carbon in this way, it can be accomplished by adjusting the carbon and hydrogen content ratio of the hydrocarbon-based gas component.

(6) Features of the DLC thin film used in the present invention;
The DLC thin film unique to the present invention formed on the surface of the substrate by the apparatus and the processing method has the following characteristics.
(A) According to the DLC thin film peculiar to the present invention, since this thin film is coated directly on the surface of the “sa” substrate containing Cr, it is excellent in wear resistance and adhesion. Can be manufactured.
(B) The DLC thin film unique to the present invention has good water repellency. Therefore, water-soluble glue that adheres to fibers and raw yarns is difficult to adhere, and even if the glue adheres, it can be easily washed away with water, so washing with an alkaline aqueous solution that is a source of environmental pollution Is no longer necessary.
(C) Since the DLC thin film peculiar to the present invention is formed directly on the substrate surface (etched metal surface), there is no oxide film that causes pores in the DLC thin film. There are no pores even in the state of a thin film, and even when immersed in an acid or alkaline solution, the substrate is not corroded or red rust is not generated.
(D) Since the DLC thin film that is unique to the present invention has a hardness of about 1000 to 2700 in addition to flexibility, the DLC thin film is worn even if it is in contact with fibers or raw yarns over a long period of time. There are few things. In addition, the DLC thin film unique to the present invention having such characteristics is preferably formed by coating the surface of the “Osa” substrate to a thickness of 1.5 to 10 μm. The reason for this is that if the thickness is less than 1.5 μm, the lifetime as “osa” cannot be sufficiently obtained. On the other hand, even if the thickness is increased to 10 μm or more, the above-mentioned performance is not significantly improved. Is not a good idea.

Example 1
In this example, in order to find suitable base material conditions, the adhesion of DLC thin films formed on the surfaces of steel, non-ferrous metal and other metal films having different chemical components was evaluated by a scratch test. did.

(1) Test specimens The following metal materials and metal surface treatment films were used as test specimens.
(A) Steel base material: SS400 steel, STBA24 steel, STBA26 steel, SUS304 steel, SUS316 steel, SUS310 steel, SUS329JI steel, SUS405 steel, SUS430 steel (b) Nonferrous metal base material: NCF600, NW2200, C1200
(C) Electroplating substrate: Cr plating film on SS400 steel with a thickness of 100 μm (d) PVD coated substrate: Mo, Nb, Ta, Si, W formed on SUS304 steel with a thickness of 2 μm The dimensions are 15 mm width × 30 mm length × 1 mm thickness, and the symbols for the steel and non-metallic materials are all JIS standards.

(2) Formation method of DLC thin film The surface of the test substrate was coated with a 2 μm-thick DLC thin film by plasma CVD after plasma etching.

(3) Scratch test method The scratch test was performed according to the test method for evaluating the adhesiveness of the ceramic thin film prescribed | regulated to ISO20502.

(4) Evaluation method After the test, the surface of the DLC thin film that has been wrinkled with a diamond needle is recorded with a photograph shown in FIG. To 4 were prepared to determine the adhesion of the DLC thin film.

(5) Test results The test results are summarized in Table 2. In this table, together with the effective component (Cr content) calculated from the amount of chemical component of the test substrate, the evaluation values of the scratch test are collectively shown.
As is clear from this result, the adhesion of the DLC thin film (Nos. 13 to 18) formed on the metal thin film such as Cr, Mo, Nb, Ta, Si, W is very good, and minute peeling is observed. Was not. On the other hand, the adhesion evaluation of the DLC thin film (Nos. 10 to 12) formed on the non-ferrous alloy substrate containing a large amount of Ni and Cu belonged to 4, and large peeling occurred around the scratches. Moreover, even if it is a steel base material, SS400 steel (No. 1) and STBA24 steel (No. 2) have relatively low adhesion of the DLC thin film (Evaluation 3). On the other hand, in the steel types (Nos. 3-5, 7-9) having an active ingredient amount of 7 mass% or more, minute peeling is recognized around the scratches, and adhesion with practically sufficient strength. It was found to have strength (Evaluation 2). However, the adhesion of the DLC thin film on the surface of the SUS310 steel substrate (No. 6) was judged to be evaluation 3 slightly lower than the former.

From the above results, in the present invention, when the base material for directly forming the DLC thin film is limited to steel materials, the effective component amount calculated by the following formula from the chemical component content of the base material is 7 mass%. The above steel types were found to be compatible materials.
Active ingredient amount = (Cr + Mo) amount in steel− (Ni + Cu) amount in steel = 7 mass%

(Example 2)
In this example, a DLC thin film having a different hydrogen content is formed on the surface of a stainless steel (SUS304 steel) base material having an active ingredient amount of 7 mass% or more, and the hydrogen content and resistance to bending deformation of the base material are formed. And investigate the change of corrosion resistance and elucidate the preferred hydrogen content of DLC thin film.

(1) Properties of the test substrate and DLC thin film The test test piece was stainless steel (SUS304 steel), and a test piece of dimensions: width 15 mm × length 70 mm × thickness 1.8 mm was prepared from this base material. . Thereafter, the entire surface of the test piece was polished to Ra: 0.08 μm, Rz: 0.09 μm, and after this plasma etching treatment, the hydrogen content was 5 to 32 atomic% and the balance was a carbon component. A DLC thin film was coated to a thickness of 3.0 μm.

(2) Test method and its conditions Bending deformation was applied 180 ° from the center of the test piece on which the DLC thin film was formed (U-bend shape), and the appearance of the DLC thin film at the bent portion was observed with a 20-fold magnifier. Moreover, the test piece after the bending test after the observation was immersed in an aqueous NaOH solution adjusted to pH (hydrogen ion concentration) 12 at a temperature of 20 ° C. for 96 hours to examine the alkali resistance of the DLC thin film and the substrate. Further, as an acid resistance test, the bending test piece was immersed in a 5% HCl aqueous solution at 20 ° C. for 96 hours, and changes in the thin film and the acid aqueous solution were observed.

(3) Test results Table 3 summarizes the test results. As is clear from this test result, the DLC thin film with a low hydrogen content (No. 1, 2, 3) generates cracks or a small area when deformed by 180 °. The thin film was observed to peel off. It can be seen that these DLC thin films have poor flexibility. On the other hand, even if the test specimen after the bending test is immersed in an alkaline aqueous solution of PH12, the test specimen is not changed at all, and the state before immersion is maintained, and the resistance to alkali resistance is sufficient. It was confirmed that In the test piece immersed in 5% HCl, the 5% HCl aqueous solution immersed in only the DLC thin film having a hydrogen content of 13 atomic% or less (No. 3) changed from colorless to pale yellow. This discoloration is presumed to be a result of the aqueous HCl solution penetrating into the interior from the defective portion of the DLC thin film that was generated during bending deformation and eroding SUS304 steel. No abnormality was observed in the DLC thin film (Nos. 4 to 7) having a hydrogen content of 15 to 32 atom%, and performance excellent in acid resistance was exhibited. However, as the DLC thin film (No. 7) with a higher hydrogen content becomes softer, quality control becomes difficult and there is a risk of a decrease in wear resistance. Therefore, in the present invention, the hydrogen content is in the range of 13 to 22 atomic%. It was confirmed that it was effective.

Example 3
In this example, the surface roughness of a SUS410 steel (Cr: 11.50-13.50 mass%, effective component amount ≦ 7 mass%) base material and the corrosion resistance of the DLC thin film formed on the surface were investigated.

(1) Test base material As a test base material, a SUS410 steel test piece having a width of 15 mm, a length of 30 mm, and a thickness of 2 μm was prepared, and then the surface thereof was polished to the following roughness.
Ra: 0.05-1.1 μm Ra: 0.09-4.8 μm

(2) DLC thin film formation method and film thickness The DLC thin film was formed by coating the DLC thin film with a thickness of 0.2 to 10 μm using the plasma CVD method. The influence of the presence or absence of the etching process can also be evaluated.

(3) Corrosion resistance test method A test piece coated with a DLC thin film was immersed in a 3% HCl aqueous solution at 18 ° C. for 100 hours, then lightly washed with water, and then the test piece was further washed at room temperature of 20 ° C. for 24 hours. Left for hours. Corrosion resistance was evaluated by the presence or absence of red rust generated on the surface of the test piece by this operation. In this test, it was washed with water after acid immersion and then left in the room because the presence of defects in the DLC thin film clearly reveals the occurrence of red rust as compared with the case of acid immersion alone.

(4) Test results The test results are summarized in Table 4. When the corrosion resistance of the DLC thin film is evaluated from the combination of the roughness of the substrate surface and the presence or absence of the plasma etching treatment, it is as follows.
(A) In general, the DLC thin film formed on the surface of the base material subjected to the plasma etching process forms a film having excellent corrosion resistance as compared with the case where the plasma etching process is not performed.
(B) The DLC thin film formed on the surface of the base material having a small surface roughness is superior in corrosion resistance as compared to the film formed on the surface of the base material having a large surface roughness. That is, it can be said that a DLC thin film with few defects is easily formed.
(C) The corrosion resistance of the DLC thin film having the same thickness is the best when the surface roughness is small and the plasma etching treatment is performed.
(D) From the above test results, if the roughness of the substrate surface is in the range of Ra: 0.05 to 0.5 μm and Rz: 0.09 to 1.5 μm, the plasma etching treatment is performed under the conditions. Thus, it was found that it is possible to select a DLC thin film having excellent corrosion resistance when the thickness of the DLC thin film is within a range of 0.5 to 10 μm.

Example 4
In this example, the adhesion of the DLC thin film formed on the surface of the SUS410 steel substrate and the effect of the plasma etching treatment as a pretreatment were investigated.

(1) Test base material The same base material as the SUS410 steel described in Example 1 was used as a test base material.
(2) Formation method and film thickness of DLC thin film The thin film was formed by the same method as Example 1, and it was set as 2 micrometers in film thickness.
(3) Adhesion test method of DLC thin film The adhesion of the DLC thin film was evaluated by a scratch test defined in ISO 20502 performed in Example 1.
(4) Test results Table 5 shows the test results. As is apparent from this result, the adhesion of the DLC thin film tested was evaluated as 2 and 4 according to the determination from the scratch state of the local DLC thin film generated in and around the scratches shown in FIG. Can be classified. However, the adhesion evaluation of the thin film formed on the surface of the test piece subjected to plasma etching pretreatment maintained evaluation 2 even when the film thickness increased, whereas the adhesion when no pretreatment was performed. When the film thickness is increased, the evaluation becomes Evaluations 3 and 4, and the tendency for the adhesion to decrease is recognized. The reason for this is that as the DLC thin film becomes thicker, the residual stress generated in the film increases, so that the residual stress of the thin film is released even by the occurrence of a slight scratch flaw, and this causes a minute peeling. it is conceivable that.

(Example 5)
In this embodiment, the durability of the coating is improved by running at high speed while contacting the yarn of the alloy fiber against the surface of “osa” on which three types of surface treatment films including the DLC thin film according to the present invention are formed. investigated.

(1) Test specimen and surface treatment coating A DLC thin film suitable for the present invention is 2.0 μm on the surface of “SUS” (dimensions: width 6 mm × length 90 mm × thickness 0.5 mm) made of SUS410 steel. The thing coated to the thickness of was prepared. The hydrogen content of this DLC thin film was 14 atomic%, the balance was carbon, and the hardness was Hv = 2050.
As a comparative surface treatment film, the following film was formed on the entire surface of “OSA”.
(A) Electric Cr plating film (thickness 5 μm)
(B) Cr ₂ O ₃ film by chemical densification method (thickness 3 μm)

  FIG. 5 shows an outline of the test method. The installation point of the other driving bobbin 54 is provided slightly below from the bobbin 53 so that the “osa” 51 on which the surface treatment film is formed contacts the surface, and the bobbin 54 is rotated at a high speed. The abrasion resistance of the film was evaluated. The running speed of the yarn was 100 mm per minute, the yarn material was polyester (tetron), and the test was conducted for 3 hours.

(3) Test results As a result of observing the surface state of “OSA” using a 20 × magnifier after the test was completed, the surface of the electroplated Cr film of the comparative example already had a dent in the film in contact with the yarn. Clearly confirmed, and also in the Cr ₂ O ₃ film, formation marks of the recesses were observed. However, no abnormality was observed on the surface of the DLC thin film according to the present invention, and the sound state was maintained.

  The loom member and the manufacturing method thereof according to the present invention are not limited to loom parts such as natural yarn such as cotton and silk, wool and synthetic fiber, but include fibers such as fishing line, hemp and jute, nets and the like. It is also effective when manufacturing. Furthermore, it can also be used for fabrics of new material fibers including metal wires such as soft copper and aluminum.

21 “Osa” base material 22 Roughness indicated by Ra 23 Roughness indicated by Rz 24 DLC thin film 25 Roughness convexity indicated by Rz that could not be covered with DLC thin film 31 Reaction vessel 32 Processed Body ("Osa" base material)
33 Conductor 34 High-voltage pulse generating power source 35 Plasma generating power source 36 Superimposing devices 37a and 37b Valve 38 Ground wire 39 High voltage introduction terminal 51 "Osas" for testing
52 Thread for test 53 Thread spool 54 Thread spool for driving

Claims (10)

A member for a loom, comprising a surface of a polished and activated steel base material directly coated with an amorphous carbon hydrogen solid deposition film. The steel substrate is made of stainless steel in which the sum of the mass contents of Cr and Mo is 7 mass% or more than the sum of the mass contents of Ni and Cu contained in the same substrate. The member for a loom according to claim 1.   The steel substrate is activated by plasma etching in an inert gas having a polished surface with Ra ≦ 0.5 μm, Rz ≦ 1.5 μm, and pressure: 0.1 to 1.0 Pa. The loom member according to claim 1 or 2, wherein the loom member has an open surface. The member for a loom according to any one of claims 1 to 3, wherein the carbon hydrogen solid deposit film has a thickness in a range of 1.5 to 10 µm. The carbon hydrogen solid deposit film is characterized in that the amount of hydrogen contained in the film is 13 to 22 atomic%, the balance is carbon, and the hardness is in the range of Hv: 1000 to 2700. The member for looms of any one of 1-4. The surface of the steel substrate is polished and finished to a smooth surface, and then the steel substrate is set to a negative potential in an inert gas and plasma etching is performed to perform the plasma etching treatment. The material surface is activated, and then the substrate is set to a negative potential in the same atmosphere, then a hydrocarbon gas is supplied, and a high-frequency high voltage pulse is applied to the substrate surface directly. A method for producing a member for a loom characterized by forming a film composed of a deposited layer of fine particles by vapor-depositing amorphous carbon-hydrogen solid fine particles containing carbon and hydrogen as main components. The steel substrate is made of stainless steel in which the sum of the mass contents of Cr and Mo is 7 mass% or more than the sum of the mass contents of Ni and Cu contained in the same substrate. The manufacturing method of the member for looms of Claim 6 characterized by these. The method of manufacturing a member for a loom according to claim 6 or 7, wherein the carbon hydrogen solid deposit film has a thickness in a range of 1.5 to 10 µm. The carbon hydrogen solid deposit film is characterized in that the amount of hydrogen contained in the film is 13 to 22 atomic%, the balance is carbon, and the hardness is in the range of Hv: 1000 to 2700. The manufacturing method of the member for looms of any one of 6-8.   The steel substrate is activated by plasma etching in an inert gas having a polished surface with Ra ≦ 0.5 μm, Rz ≦ 1.5 μm, and pressure: 0.1 to 1.0 Pa. The loom member according to any one of claims 6 to 9, wherein the loom member has a curved surface.

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