WO2018142487A1

WO2018142487A1 - Article having metallic surface, tone-treatment method therefor, and gas phase oxidation device

Info

Publication number: WO2018142487A1
Application number: PCT/JP2017/003473
Authority: WO
Inventors: 優二中村; 俊孝若林; 郁恵山口; 尚子小林; 宮崎　邦夫
Original assignee: Ykk株式会社
Priority date: 2017-01-31
Filing date: 2017-01-31
Publication date: 2018-08-09
Also published as: CN110234782B; TWI666342B; TW201829841A; EP3578681A1; EP3578681A4; CN110234782A

Abstract

The present invention improves rubbing fastness after a tone treatment has been performed on an article having a base material where at least the surface is composed of copper-zinc alloy. The present invention also provides a tone-treatment device that makes it possible to keep the amount of water used lower than with a wet treatment. Provided is an article having a base material 11 where at least the surface is composed of a copper alloy containing zinc, and an oxide layer 12 adjacent to the base material 11 surface, a ratio A of the mean zinc concentration to the mean copper concentration in a range of the depth of 10 to 20 nm with reference to the oxide layer 12 surface being higher than a ratio B of the mean zinc concentration to the mean copper concentration in the base material 11 surface. Also provided is a gas phase oxidation device for carrying out a tone-treatment method, the gas phase oxidation device being provided with: a gas phase reaction chamber 115 having an entrance and an exit and carrying out gas phase oxidation; and a conveyance mechanism 122 with which an elongated member, at least a part of which is provided with a portion where at least the surface is composed of metal, enters from the entrance, passes through the inside of the gas phase reaction chamber 115, and continuously comes out from the exit.

Description

Article having metal surface, color tone processing method thereof, and vapor phase oxidation apparatus

The present invention relates to an article having a metal surface, and more particularly to a metal fastener member. The present invention also relates to a color tone processing method for an article having a metal surface, and more particularly to a color tone processing method for a metal fastener member. Furthermore, the present invention relates to a gas phase oxidation apparatus for carrying out a color tone processing method for a long article having a metal surface.

Among fasteners, there are products called metal fasteners that make up elements (engagement elements) with metals such as red brass, brass, white and aluminum, among which representatives are red, brass, and white. Metal fasteners using copper-zinc alloys are widely used because they can balance price, strength, hardness and workability. In the fashion field that handles clothing and clothing, fasteners are required not only to have excellent functionality but also to have a design that matches the design of the article. Therefore, it is required to provide a metal fastener member having a large number of colors so that it can be used for various article designs.

Conventionally, the method for color tone treatment of a metal surface includes a method of surface coating with an organic paint, a method of changing the color tone by changing the composition or plating a metal of a different composition on the surface, and There is a method of coloring the surface to a specific color by performing some chemical conversion treatment, and all of them are mainly performed by a color treatment by a wet treatment.

For example, Japanese Patent Application Laid-Open No. 2014-205881 (Patent Document 1) describes a treatment method in which the appearance of a surface is colored in a blue color by immersion in a chlorite-based chemical conversion treatment solution. Specifically, the copper-based metal is immersed in a chlorite-based chemical conversion treatment solution containing 0.5 to 250 g / L of chlorite and 1 to 625 g / L of an alkali metal hydroxide. A characteristic blue color treatment method for copper-based metal surfaces is described. In the Examples, it is described that a chemical conversion treatment was performed after copper plating was applied to a button top part member made of brass.

JP 2014-205881 A

If the chemical conversion treatment described in Patent Document 1 is performed, the surface of the copper-zinc alloy can be colored blue. However, according to the examination results of the present inventors, it has been found that when the above chemical conversion treatment is performed on an article made of a copper-zinc alloy, there arises a problem that the friction fastness is lowered. In order to provide a wide lineup of copper-zinc alloy articles, it is desirable to be able to adjust the copper-zinc alloy articles to various colors without sacrificing friction fastness.

Therefore, an object of the present invention is to improve the fastness to friction after color tone treatment is performed on an article having a base material having at least a surface composed of a copper-zinc alloy.

In addition, when performing color tone processing by wet processing, the chemical treatment uses a large amount of chemicals, which increases the load of wastewater treatment, and is difficult to implement in areas where water resources are scarce. There are various problems such as being easy to do.

Therefore, another object of the present invention is to provide an apparatus for color tone processing that can reduce the drainage load as compared with wet processing.

The present inventor observed the cross section near the surface of the copper-zinc alloy with an electron microscope after performing color tone treatment by chemical conversion treatment on the surface of the copper-zinc alloy, and the cross section was observed in various places. It was found that the porous structure had voids. It is presumed that the porous structure is caused by the following chemical reaction near the surface by the chemical conversion treatment: Zn + 2OH ⁻ + 2H ₂ O → [Zn (OH) ₄ ] ²⁻ , resulting in dezincification.

Based on the above inference, the present inventor has intensively studied the surface structure for improving the friction fastness in a copper-zinc alloy article having a changed color tone, and has adjusted the color tone to a dense oxide layer in which zinc is concentrated on the outermost surface. It was found that providing a function to change is effective in solving the problem.

The present invention has been completed on the basis of the above findings. In one aspect, the present invention includes a base material having at least a surface made of a copper alloy containing zinc, and an oxide layer adjacent to the surface of the base material. The ratio A of the average zinc concentration to the average copper concentration in the range from the depth of 10 nm to the depth of 20 nm with reference to the oxide layer surface is higher than the ratio B of the average zinc concentration to the average copper concentration on the substrate surface. Is also a high article.

In an embodiment of the article according to the present invention, the average zinc concentration on the surface of the substrate is 5 to 50 at. %.

In another embodiment of the article according to the present invention, the ratio A / B of the ratio A to the ratio B is 2.0 or more.

In yet another embodiment of the article according to the present invention, the entire substrate is made of a copper alloy containing zinc.

In yet another embodiment of the article according to the present invention, the average zinc concentration in the range from a depth of 10 nm to a depth of 20 nm is 5 to 80 at. %.

In yet another embodiment of the article according to the present invention, the article is a slide fastener member.

In another aspect, the present invention is a slide fastener including the slide fastener member according to the present invention.

In yet another aspect, the present invention is a color tone treatment method for an article, comprising vapor-phase oxidation of an article having a substrate made of a copper alloy containing zinc at least on the surface in the presence of at least oxygen. .

In one embodiment of the color tone processing method according to the present invention, an average copper concentration in the range from a depth of 10 nm to a depth of 20 nm, which is an oxide layer adjacent to the surface of the base material. Forming an oxide layer by vapor phase oxidation in which the ratio A of the average zinc concentration to the A is higher than the ratio B of the average zinc concentration to the average copper concentration on the substrate surface.

In another embodiment of the color tone processing method according to the present invention, the gas phase oxidation is performed in the presence of ammonia.

In yet another embodiment of the color tone processing method according to the present invention, the color tone control by the gas phase oxidation is performed by adjusting the ammonia concentration, the oxygen concentration, the concentration of other reactive gases, the humidity in the reaction system, It is carried out by changing one or more selected from the group consisting of the temperature inside, the processing time, and the temperature of the article.

In yet another embodiment of the color tone processing method according to the present invention, the article is a fastener member.

In yet another embodiment of the color tone processing method according to the present invention, the gas phase oxidation is performed at an ambient temperature of 20 to 80 ° C.

In yet another embodiment of the color tone processing method according to the present invention, the gas phase oxidation is performed under a negative pressure.

In yet another embodiment of the color tone processing method according to the present invention, before performing the gas phase oxidation, the substrate surface is sequentially subjected to activation treatment and water washing.

In yet another embodiment of the color tone processing method according to the present invention, before the vapor phase oxidation is performed, degreasing and water washing are sequentially performed on the substrate surface.

In still another embodiment of the color tone processing method according to the present invention, at least one or more selected from the group consisting of clear coating, rust prevention treatment and waxing on the surface of the oxide layer formed by the gas phase oxidation. Performing a surface treatment.

According to still another aspect of the present invention, a gas phase reaction chamber for performing gas phase oxidation having an inlet and an outlet, and a long member having at least a part of which at least a surface is made of metal enter from the inlet. A transport mechanism for passing through a phase reaction chamber and continuously exiting from the outlet, a discharge port for supplying a gas-phase oxidizing gas into the gas-phase reaction chamber, and the gas-phase reaction chamber It is a gas phase oxidation apparatus for carrying out a color tone processing method provided with a suction port for discharging the gas inside the chamber.

In one embodiment of the gas phase oxidation apparatus according to the present invention, a water seal unit for shutting off gas inside the gas phase reaction chamber is provided at either or both of the outlet side and the inlet side of the gas phase reaction chamber. is set up.

In another embodiment of the gas phase oxidation apparatus according to the present invention, a water seal unit for shutting off gas inside the gas phase reaction chamber from the outside is installed only on the outlet side of the gas phase reaction chamber.

In yet another embodiment of the vapor phase oxidation apparatus according to the present invention, an air flow control mechanism is provided for controlling the vapor phase oxidation gas supplied into the vapor phase reaction chamber to flow from the inlet side to the outlet side. .

In still another embodiment of the vapor phase oxidation apparatus according to the present invention, the air flow control mechanism includes at least one discharge port for supplying a vapor phase oxidation gas installed in the vapor phase reaction chamber. , Including at least one suction port for discharging the gas in the chamber to the outside of the chamber, wherein all the suction ports of the at least one suction port are more than all the discharge ports of the at least one discharge port. Is also arranged on the exit side.

In still another embodiment of the vapor phase oxidation apparatus according to the present invention, the transport mechanism may be configured such that one or both of a substantially vertical upward direction and a substantially vertical downward direction as a direction in which the article passes through the gas phase reaction chamber. It is configured to be included.

In yet another embodiment of the gas phase oxidation apparatus according to the present invention, the gas phase reaction chamber includes a first chamber on the inlet side, a second chamber on the outlet side, and a first chamber and a second chamber. A third chamber in between, and the transport mechanism is configured so that the article can sequentially pass through the first chamber, the third chamber, and the second chamber, and the article passes through the third chamber. One or both of a substantially vertical upward direction and a substantially vertical downward direction are included as the direction to perform.

In yet another embodiment of the vapor phase oxidation apparatus according to the present invention, the third chamber is located above the third chamber upper portion and the third chamber upper portion at the same height as the first chamber and the second chamber. A lower part of the third chamber is provided, and the transport mechanism is configured to allow the article to pass through the first chamber, the third chamber upper part, the third chamber lower part, and the second chamber.

In yet another embodiment of the vapor phase oxidation apparatus according to the present invention, at least one discharge port is provided in the lower portion of the third chamber, and at least one of the suction ports is provided in the second chamber.

In still another embodiment of the vapor phase oxidation apparatus according to the present invention, the transport mechanism includes both a substantially vertical upward direction and a substantially vertical downward direction as directions in which the article passes through the third chamber. It is configured.

According to the present invention, it is possible to improve the friction fastness in an article made of a copper-zinc alloy whose surface has a changed color tone. Friction fastness is an important characteristic especially when considering application to metal fastener members, and it is possible to impart color change to copper-zinc alloy fastener members without sacrificing friction fastness. Is of great commercial significance. In addition, according to the present invention, it is possible to easily change an article having a copper-zinc alloy on the surface in various colors by changing the kind and ratio of the oxide constituting the oxide layer. Moreover, in the article according to the present invention, since Zn remains in the vicinity of the surface, there is also an advantage that the color tone can be changed using Zn. That is, in the conventional chemical conversion treatment, the elements involved in the color tone change are mainly Cu and O because dezincing near the surface. According to the present invention, since zinc remains on the surface, Cu and In addition to O, Zn can also participate in the color tone change, and various color tones can be obtained. For this reason, this invention is advantageous also in the point which enables various goods expansion | deployment. Moreover, the vapor phase oxidation apparatus according to the present invention basically does not require the use of water in the reaction chamber.

It is the figure which showed typically an example of the cross-section of the article | item concerning this invention. It is the figure which showed typically another example of the cross-section of the article | item concerning this invention. 10 is a graph showing a depth profile of atomic concentrations of O, Cu, and Zn when AES analysis is performed on the element surface of Test Example 3. FIG. 10 is a graph showing a depth profile of atomic concentrations of O, Cu, and Zn when AES analysis is performed on the element surface of Test Example 6. FIG. 1 is a schematic front view showing a first embodiment of a vapor phase oxidation apparatus according to the present invention. It is a front schematic diagram which shows 2nd embodiment of the gaseous-phase oxidation apparatus which concerns on this invention. It is a front schematic diagram which shows 3rd embodiment of the vapor-phase oxidation apparatus which concerns on this invention. It is a front schematic diagram which shows the apparatus structural example of the color tone processing system which concerns on this invention.

<1. Article>
In one embodiment, an article according to the present invention has a base material having at least a surface made of a copper alloy containing zinc. As the copper alloy containing zinc, copper-zinc alloys such as brass, red copper, and white and copper-zinc-nickel alloys are excellent in terms of strength, cost, and workability, and can be suitably used. For example, the copper alloy containing zinc contains 1 to 40% by mass, preferably 4 to 40% by mass of Zn, and is selected from Ni, Be, Mo, Al, Sn, Pb, Mn, Fe, P and S. One or more elements may be contained in an amount of 0 to 10% by mass, and the composition may be composed of the balance copper and inevitable impurities. The base material should just be comprised by the copper alloy in which the surface contains zinc at least, and the case where the inside is comprised by resin, ceramic, etc. by laminated structure is included. Of course, the substrate may be composed of a copper alloy containing zinc as a whole including not only the surface but also the inside.

Although there are no particular restrictions on the use and type of the article according to the present invention, a metal fastener member can be used in a typical embodiment. Examples of the metal fastener include a slide fastener and a snap fastener. Further, as a field other than metal fasteners, ball chains and the like can be cited. Examples of the member for the slide fastener include, but are not limited to, an element (engagement element), a slider, a handle, an upper stopper, a lower stopper, and a release fitting. Examples of the member for the snap fastener include a male element and a female element. The metal fastener member may be in the final part shape to be attached to the fastener product as described above, or may be in the form of a wire, a plate, a tube, a rod or the like before being processed.

FIG. 1 schematically shows a cross-sectional structure of an embodiment of an article according to the present invention. The article 10 has a base material 11 and an oxide layer 12 adjacent to the surface of the base material 11. In the present embodiment, the ratio A of the average zinc concentration to the average copper concentration in the oxide layer 12 is higher than the ratio B of the average zinc concentration to the average copper concentration on the surface of the substrate 11. That is, zinc is concentrated in the oxide layer 12. This means that dezincification does not occur in the oxide layer 12, and it is possible to suppress the oxide layer 12 from exhibiting a porous structure. The average zinc concentration and average copper concentration of the oxide layer 12 are analyzed by elemental analysis in the depth direction by Ar ion etching from the oxide layer surface by AES (Auger Electron Spectroscopy), and the total number of atoms of Cu, Zn and O is calculated. It is expressed by the average atomic concentration of Zn and the average atomic concentration of Cu in the range from a depth of 10 nm to a depth of 20 nm with reference to the oxide layer surface when 100%. In the present invention, the depth when the composition analysis in the depth direction by AES refers to the depth when converted from the sputtering time using the etching rate of 8.0 nm / min of the SiO ₂ standard material (the same applies to the following). is there.). Note that if there is no finishing layer 13 to be described later on the oxide layer 12, the oxide layer 12 becomes the outermost layer.

In a preferred embodiment of the article according to the present invention, the ratio A / B of the ratio A in the oxide layer 12 to the ratio B on the surface of the substrate 11 is greater than 1.0, and the ratio is 1.5 or more. It can also be 2.0 or more, for example, 1.2 to 3.0.

In one embodiment of the article according to the present invention, the average zinc concentration in the range from a depth of 10 nm to a depth of 20 nm with reference to the surface of the oxide layer 12 is 5 at. % Or more, and in a more typical embodiment 10 at. % Or more. In one embodiment of the article according to the present invention, the average zinc concentration in the range from a depth of 10 nm to a depth of 20 nm, based on the surface of the oxide layer 12, is 80 at. % Or less, and in a more typical embodiment 60 at. % Or less, and in an even more typical embodiment 40 at. % Or less, and in an even more typical embodiment, 30 at. % Or less. The average zinc concentration of the oxide layer 12 is determined by analyzing the composition from the surface of the oxide layer in the depth direction by AES (Auger electron spectroscopy), and the total number of atoms of Cu, Zn and O is 100%. Expressed in concentration.

In one embodiment of the article according to the present invention, the average oxygen concentration in the range from a depth of 10 nm to a depth of 20 nm with reference to the surface of the oxide layer 12 is 20 at. % And in typical embodiments 20-60 at. %, And in a more typical embodiment 30-50 at. %. The average oxygen concentration of the oxide layer 12 is determined by composition analysis in the depth direction from the surface of the oxide layer by AES (Auger electron spectroscopy), and the total number of Cu, Zn and O atoms is 100%. Expressed in concentration.

In the present invention, the boundary between the oxide layer and the substrate is analyzed by AES (Auger Electron Spectroscopy) in the depth direction from the oxide layer surface toward the substrate, and the total number of atoms of Cu, Zn, and O is calculated. When the atomic concentration of O is 5 at. Points to the first depth point to reach below%. In addition, another layer (finishing layer) may be formed on the oxide layer, and the definition of the surface of the oxide layer (between another layer and the oxide layer) in that case will be described later.

The average zinc concentration on the substrate surface is 5 at. % Or more, preferably 10 at. % Or more is more preferable. In addition, the average zinc concentration on the substrate surface is 50 at. % Or less, preferably 40 at. % Or less is more preferable. The average zinc concentration and average copper concentration on the substrate surface were analyzed in the depth direction from the substrate surface to a depth of 20 nm by AES (Auger Electron Spectroscopy), and the total number of Cu, Zn and O atoms was 100%. The average atomic concentration of Zn and the average atomic concentration of Cu from the surface of the substrate to the depth are expressed respectively.

Even when the whole substrate is made of a copper alloy containing zinc, the average zinc concentration in the whole substrate is 5 at. % Or more, preferably 10 at. % Or more is more preferable. Moreover, the average zinc concentration in the whole substrate is 50 at. % Or less, preferably 40 at. % Or less is more preferable. The average zinc concentration in the entire substrate is expressed by the atomic concentration of Zn when the total number of Cu, Zn and O atoms in the entire substrate is 100%, and can be analyzed by a fluorescent X-ray analyzer.

FIG. 2 schematically shows a cross-sectional structure of another embodiment of the article according to the present invention. The article 20 has a base material 11, an oxide layer 12 adjacent to the surface of the base material 11, and a finishing layer 13 adjacent to the surface of the oxide layer 12. This embodiment is different from the embodiment of FIG. 1 in that a finishing layer 13 is formed on the oxide layer 12. Examples of the finishing layer 13 include at least one or more surface treatment layers formed of one or more surface treatment agents such as a clear lacquer, a rust inhibitor, and a wax. The surface-treated surface preparations may be used alone or in combination of two or more. The finishing layer may be a single layer or a plurality of layers.

Although it does not restrict | limit especially as a chemical | medical agent for clear lacquer coating, For example, 1 type, or 2 or more types of resin components selected from an acrylic resin, a polyester resin, an alkyd resin, a urethane resin, an epoxy resin, etc., block polyisocyanate, Examples thereof include one prepared by dissolving or dispersing one or two or more kinds of crosslinking agents selected from melamine resin, urea resin and the like and other additives in an organic solvent or water. Although it does not restrict | limit especially as a chemical | medical agent for a rust prevention process, For example, a benzotriazole type | system | group, a phosphate ester type | system | group, and an imidazole type | system | group are mentioned. Although it does not specifically limit as a chemical | medical agent for wax, Usually, a paraffin can be made into a main component and a conventional wax component can be added as needed.

When the finishing layer is present, the average copper concentration and the average zinc concentration in the oxide layer 12 and the average copper concentration and the average zinc concentration on the surface of the base material 11 are measured up to the base material surface while etching the finishing layer in the depth direction. It can be measured by AES analysis. Further, when the finishing layer is thick, it can be measured by removing the finishing layer just before the oxide layer and similarly performing AES analysis in the depth direction.

The finishing layer can be removed with a release agent in some cases. As the release agent, for example, the product can be released by immersing the article in the trade name “Esvac H-300” (manufactured by Sasaki Chemical) at room temperature overnight. In addition, the immersion time of the release agent can be changed according to the thickness of the finishing layer. However, if the oxide layer is removed in addition to the finish layer, the boundary between the finish layer and the oxide layer disappears. Therefore, it is desirable to remove the finish layer so that a part of the finish layer remains.

The boundary between the finish layer and the oxide layer can be identified by changes in Cu and Zn concentrations. Cu and Zn are hardly detected in the finished layer, but much Cu and Zn are detected in the oxide layer. Therefore, in this specification, the depth point where the sum of the atomic concentrations of Cu and Zn when the AES analysis in the depth direction first reaches 1% or more is defined as the boundary between the finishing layer and the oxide layer. The atomic concentration of Cu and Zn is represented by the ratio of the number of atoms of Cu and Zn to the total number of atoms of Cu, Zn and O.

<2. Manufacturing method of article>
The article according to the present invention can be manufactured, for example, by subjecting the surface of the base material to vapor phase oxidation. Vapor phase oxidation is advantageous in that it can remarkably reduce the environmental load caused by harmful substances and wastewater treatment costs, and the oxidation reaction conditions can be easily changed. Hereinafter, specific embodiments of the gas phase oxidation will be described in detail. Vapor phase oxidation can be performed on a single member of the base material, or can be performed on the base material bonded to other parts. For example, when the base material is a slide fastener element, gas phase oxidation is applied to a fastener stringer in which a row of slide fastener elements is attached to a fastener tape or a fastener chain in which a pair of fastener stringer element rows are engaged with each other. Can be implemented.

(2-1 Pretreatment)
Pretreatment is preferably performed before vapor phase oxidation of the surface of the substrate. This is because the effect of improving the reactivity and uniformity of gas phase oxidation can be obtained depending on the kind of pretreatment. Specific examples of the pretreatment method include metal activation treatment. By performing the metal activation treatment, the reaction efficiency during the gas phase oxidation can be improved.

There are both wet and dry methods for the metal activation treatment.
Examples of the wet method include a method in which an acidic or alkaline aqueous solution is brought into contact with the surface of the base material for treatment. Examples of acidic aqueous solutions include aqueous solutions of inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, chromic acid, and phosphoric acid, and aqueous solutions of organic acids such as acetic acid and dibasic acids (oxalic acid, malonic acid, succinic acid, and aspartic acid). Examples of the alkaline aqueous solution include ammonia water, NaOH aqueous solution, sodium carbonate, sodium silicate, etc. Among these, hydrochloric acid is preferable for acidity and NaOH aqueous solution is preferable for alkalinity from the viewpoint of removal of the oxide film after treatment. The method of bringing the acidic or alkaline aqueous solution into contact with the surface of the substrate is not limited, but immersion of the substrate in the aqueous solution, spraying, dropping, coating, roll coating of the aqueous solution on the substrate, and For example, a sink.
Examples of the dry method include plasma treatment (eg, O ₂ plasma treatment), UV ozone method, marcomizing method, halogen-based gas treatment, and the like.
In either case of wet type or dry type, it is desirable to carry out water washing from the removal of residual components after the metal activation treatment.

Before performing the pretreatment described above, it is preferable to further perform degreasing and water washing treatment on the base material in order to enhance the effect of the pretreatment. Any known degreasing method may be employed as the degreasing method, and examples thereof include a method in which the degreasing agent is brought into contact with the surface of the substrate by dipping, wiping, brushing, spraying, or the like. In soaking, rocking or ultrasonic waves may be added to enhance the degreasing effect. Furthermore, conventional surface treatments such as chemical polishing treatment, plating treatment, physical polishing treatment, and preliminary degreasing treatment may be performed before the degreasing and water washing treatment.

(2-2 Gas phase oxidation)
The method for vapor phase oxidation is not particularly limited as long as it can form a predetermined oxide layer on the surface of the substrate. Various methods can be considered for the gas phase oxidation method. For example, when copper and zinc are oxidized in the presence of oxygen, the following chemical reaction proceeds to change into copper oxide and zinc oxide. By changing the conditions of the gas phase oxidation, the oxidation state of Cu and Zn on the surface of the base material changes, whereby various color tones can be adjusted.
・ Cu + 1 / 2O ₂ → Cu ₂ O (monovalent) → CuO (divalent)
・ Zn + 1 / 2O ₂ → ZnO (divalent)
However, since the rate of the oxidation reaction is low under low temperature conditions, it is preferable to promote oxidation. The heating temperature may be increased to promote oxidation, but when the base material is combined with another material having low heat resistance, for example, when the base material is a slide fastener element, When phase oxidation is performed, there is a restriction that it is necessary to perform the heat treatment at a temperature lower than the heat resistant temperature of a synthetic fiber fastener tape or the like. For this reason, in order to promote the oxidation reaction even under low temperature conditions, it is preferable to add ammonia (NH ₃ ) as an oxidation accelerator.

Therefore, in a preferred embodiment of the color tone treatment method for a substrate according to the present invention, the gas phase oxidation is carried out in the presence of oxygen and ammonia. The method for supplying oxygen is not particularly limited, and examples thereof include a method of supplying in the form of air, oxygen gas, mixed gas of oxygen gas and inert gas (nitrogen, rare gas, etc.). The method of supplying in the form of is preferable.

Ammonia is a cheap and universal gas that can be obtained all over the world. Ammonia can be converted to nitrogen (N ₂ ) and hydrogen (H ₂ ) by thermal decomposition (NH ₃ → 1 / 2N ₂ + 3 / 2H ₂ ). Can be further converted to water (H ₂ → H ₂ O). For this reason, clean exhaust gas can be discharged. Further, the ammonia-containing water that can be produced by washing the article after vapor phase oxidation can be neutralized and converted to ammonium sulfate (fertilizer raw material). As described above, ammonia is a substance that is highly economical and has a low environmental impact.

Vapor phase oxidation can be performed at 0 to 100 ° C., for example, and can be performed at room temperature. For this reason, although it can implement without special cooling cost and heating cost, it is preferable to heat a little for acceleration of reaction. For this reason, the gas phase reaction is preferably performed at an atmospheric temperature of 20 ° C. or higher, and more preferably performed at an atmospheric temperature of 30 ° C. or higher.

In addition, gas phase oxidation can be performed under atmospheric pressure and does not need to be performed under reduced pressure or under pressure. However, from the viewpoint of safety, it is preferable to prevent leakage of internal gas such as ammonia by making the reaction chamber have a negative pressure. For this reason, it is preferable to carry out the gas phase oxidation under reduced pressure (from atmospheric pressure to slightly negative pressure).

Although not intending that the invention be limited by theory, moderately water (H ₂ O) present on the surface of the substrate and (wet state), NH ₃ is ionized to NH ₄ ^+, NH It is presumed that ₄ ⁺ binds to the metal (for example, Cu and Zn) on the surface of the fastener member to promote the oxidation reaction. Taking the oxidation of Cu as an example, it is considered that the following reaction proceeds promptly to promote the oxidation. The color tone changes due to the formation of metal oxides and hydroxides. For example, Cu ₂ O is reddish brown, CuO is black, and Cu (OH) ₂ is blue.
・ NH ₃ + H ₂ O → NH ₄ ⁺ + OH ⁻
Cu + 1 / 2O ₂ + 4NH ₃ + H ₂ O → [Cu (NH ₃ ) ₄ ] ₂ ++ 2OH ⁻
Cu ²⁺ + 2OH ⁻ → Cu (OH) ₂
Cu (OH) ₂ + O ₂ → Cu ₂ O → CuO + H ₂ O
Further, under the ammonia rich condition, the reaction of the following formula proceeds and becomes bluish.
Cu (OH) ₂ + 4NH ₃ → [Cu (NH ₃ ) ₄ ] (OH) ₂
Further, when hydrogen peroxide, which is a strong peroxide, is present, the following oxidation reaction proceeds rapidly, and the color tone can be stabilized.
Cu + H ₂ O ₂ + 4NH ₃ → [Cu (NH ₃ ) ₄ ] ²⁺ + 2OH ⁻

In the above reaction, an oxide of Zn (standard generation free energy ΔG CuO (−14)> Cu ₂ O (−35)> ZnO (−76)) having a better affinity for oxygen than Cu is formed in the outermost layer. Therefore, when vapor phase oxidation is performed while the copper-zinc alloy forms the surface of the base material, the copper-zinc alloy whose zinc ratio (Zn / Cu) in the outermost layer is the base material Although it is not intended that the present invention be limited by theory, this reaction mechanism forms a dense oxide layer by enriching Zn in the oxide layer. it is conceivable that.

In the above reaction, at least one selected from the group consisting of ammonia concentration, oxygen concentration, concentration of other reactive gases, humidity in the reaction system, temperature in the reaction system, treatment time, and article temperature. The color tone can be controlled by changing the color tone. By simply changing these parameters, multicolorization can be easily realized while using the same equipment.

When the color tone treatment is performed on the Cu—Zn alloy surface, for example, in the coloring by the conventional chemical conversion treatment using an alkali, the Zn-elution reaction (Zn + 2OH ⁻ + 2H ₂ O → [Zn (OH) ₄ ] ² + + H ₂ ) and the oxidation reaction of Cu and Zn are carried out at the same time, and the oxide film has a porous structure due to the Zn removal reaction (ionization tendency: Cu <Zn). Can be. However, according to the gas phase oxidation, zinc is only oxidized by the gas phase reaction (Zn + 1 / 2O ₂ → ZnO), and since there is no dezincification, macro voids are not observed and the film structure is denser than the chemical conversion treatment. Thus, it is possible to improve the fastness to friction.

In order to further increase the number of colors, not only oxides and / or hydroxides but also one or more compounds such as metal carbonates, sulfides and sulfates may be generated on the surface of the fastener member. In the case of copper, carbonates are yellow, green, and blue, sulfides are black, and sulfates are blue. By changing the composition ratio of these metal compounds and the depth of the surface reaction, it is possible to change to more colors. Examples of the method of generating various metal compounds on the surface of the fastener member include a method of adding a reactive substance that generates a desired metal compound during pretreatment or gas phase oxidation.

For example, as a gas to be supplied for gas phase oxidation, gas is wetted by using a gas after bubbling in water or an aqueous solution in which a desired compound that can be colored in a target color is dissolved. Therefore, the color tone can be changed. Halogen gas (Cl ₂ , Br _2, etc.), carbon dioxide (CO ₂ ), hydrogen peroxide, etc. can be added during the gas phase oxidation. The color tone can also be adjusted by using an aqueous solution of a desired compound that can be colored to the target color during the metal activation treatment. Examples of aqueous solutions include aqueous solutions of inorganic acids such as hydrochloric acid, sulfuric acid, peroxodisulfuric acid, nitric acid, chromic acid and phosphoric acid, and organic acids such as acetic acid and dibasic acids (oxalic acid, malonic acid, succinic acid, aspartic acid, etc.). Examples include aqueous solutions, carbonates, sulfates, peroxodisulfates, aqueous solutions of salts such as sulfides, and hydrogen peroxide.

After vapor phase oxidation, it is preferable from the viewpoint of removing residual components that the unreacted components (eg, ammonia) adhering to the surface of the substrate are washed with water. In addition, after the gas phase oxidation, one or more surface treatments such as rust prevention treatment, clear lacquer coating, and waxing can be performed as necessary. Although not limited, the surface treatment can be performed by immersion in each surface treatment liquid, spraying of the surface treatment liquid, dropping, coating, roll coating, and pouring.

Thus, according to the present invention, an oxide layer adjacent to the surface of the base material is obtained by subjecting an article having a base material, at least the surface of which is made of a copper alloy containing zinc, to gas phase oxidation in the presence of oxygen. A method for color-treating an article comprising forming an oxide layer in which the ratio A of the average zinc concentration to the average copper concentration in the oxide layer is higher than the ratio B of the average zinc concentration to the average copper concentration on the substrate surface Is provided. Furthermore, according to this invention, the manufacturing method of a fastener including using the color tone processing method mentioned above is provided. A slide fastener and a snap fastener can be produced by a conventional means using the fastener member subjected to the color tone processing according to the present invention. For example, when the fastener member is an element for a slide fastener, the color tone processing according to the present invention is performed in a state where the fastener chain is assembled, and then a slider, a pull handle, an upper stopper, a lower stopper, and an open / close fit by conventional means. A slide fastener is completed by appropriately attaching parts such as an insert.

(2-3 Gas phase oxidation equipment)
Next, a description will be given of a configuration example of a gas phase oxidation apparatus suitable for performing continuous color tone processing on a long object having at least a part of which the surface is made of metal as a processing target.
As a long member including at least a part of metal, a metal fastener member is an element, and a slide fastener component (fastener chain) including a fastener stringer in which a row of elements is attached to one side edge of a long fastener tape. ), Or a ball chain in which metal balls are connected, a wire-like metal fastener member, or a metal wire member. Furthermore, a slide fastener assembly in which parts such as a slider, an upper stopper, and a lower stopper are attached to the fastener chain is also included. The apparatus introduces the metal fastener member into the reaction chamber maintained at atmospheric pressure or negative pressure while continuously conveying the metal fastener member in the longitudinal direction, performs vapor phase oxidation of the member surface in the reaction chamber, and then the member It is possible to implement a color tone processing method for a long member including at least a part of which at least a surface is made of a metal, including discharging from the outlet of the reaction chamber.

<2-3-1 First Embodiment>
A configuration example of a gas phase oxidation apparatus that can be used for color tone processing according to the present invention will be described. In the description of the specific examples relating to the apparatus, the object to be treated was obtained by engaging a pair of fastener stringers in which a row of elements was attached to one side edge of a long fastener tape between opposing rows of elements. A slide fastener chain will be described as an example.

FIG. 5 schematically shows a front view of the vapor phase oxidation apparatus 110 according to the first embodiment. The gas phase oxidation apparatus 110 includes an upstream water seal unit 116, a gas phase reaction chamber 115 having an inlet 115in and an outlet 115out, a gas phase oxidation gas supply system 114, a downstream water seal unit 116, a transport mechanism 122, and a gas. A suction device 113 and an ammonia gas decomposition device 112 are provided, and the operation of these devices can be controlled by the control device 118. Corrosion resistance can be ensured by using stainless steel, particularly austenitic stainless steel, for the portion in contact with the gas phase oxidizing gas.

The fastener chain 120 continuously passes through the gas phase reaction chamber 115 inside the gas phase oxidation apparatus 110 in the direction of the arrow by the transport mechanism 122. The transport mechanism 122 includes a plurality of guide rollers 122a, and the fastener chain 120 passes through the gas phase reaction chamber 115 while being guided by the plurality of guide rollers 122a. Of the plurality of guide rollers 122a, one or more guide rollers may be connected to a drive source such as a motor and the drive roller itself may be a drive source for the fastener chain 120. Further, the drive source 122b may be provided outside the gas phase oxidation apparatus 110 and the fastener chain 120 may be conveyed by a pulling system from the outside.

The gas-phase oxidation gas supply system 114 in the first embodiment includes a gas storage unit 114a, a gas pipe 114b, and a gas discharge port 114c. The gas-phase oxidizing gas stored in the gas storage unit 114a passes through the gas pipe 114b and is supplied from the gas discharge port 114c into the gas-phase reaction chamber 115. When there are a plurality of gas phase reaction gases, a plurality of gas storage units may be provided. In the first embodiment, in addition to the gas storage unit 114a, a gas storage unit 114d is provided, and the gas-phase oxidizing gas from the gas storage unit 114d passes from the gas storage unit 114a while passing through the gas pipe 114b. Premixed with gas for gas phase oxidation. Illustratively, ammonia can be stored from the gas storage unit 114a and air can be stored from the gas storage unit 114d. The air may be compressed air from a compressor instead of the gas storage unit.

There may be one gas discharge port 114c, but a plurality of gas discharge ports 114c may be provided in order to increase reaction efficiency. Further, in order to improve the uniformity of the color tone between the front and back of the fastener chain 120, the gas discharge ports 114c are preferably installed on both sides of the fastener chain 120. Of course, when it is desired to change the color tone between the front and back of the fastener chain 120, the gas discharge port 114c can be provided only on one surface side of the fastener chain 120. In the first embodiment, a plurality of gas discharge ports 114 c are alternately arranged in both the upper surface side and the lower surface side of the fastener chain 120 in the gas phase reaction chamber 115 along the conveying direction of the fastener chain 120.

While passing through the gas phase reaction chamber 115, the fastener chain 120 is subjected to a color tone process based on an oxidation reaction in the presence of a gas phase oxidizing gas. The gas in the gas phase reaction chamber 115 is sucked from a suction port 121 installed in the vicinity of the outlet by a gas suction device 113 such as a blower, discharged through the pipe 123 to the outside of the gas phase reaction chamber 115, and an ammonia gas decomposing device. At 112, unreacted ammonia is decomposed into H ₂ O and N ₂ and then discharged out of the apparatus 110. The method for decomposing ammonia gas is not particularly limited, and examples thereof include a catalytic decomposition method, a combustion method, a gas decomposition method, and a wet scrubber method. In addition, the ammonia gas decomposing apparatus is preferably provided as necessary, but is not necessarily essential in the present invention.

By setting the suction force of the gas suction device 113 so that the gas suction amount from the suction port 121 is larger than the gas discharge amount from the discharge port 114c, the gas phase reaction chamber 115 can be maintained at a negative pressure. it can. Thereby, it is possible to prevent the gas in the gas phase reaction chamber 115 from leaking to the outside. However, a water seal unit 116 is provided on the inlet 115in side (upstream side) and / or the outlet 115out side (downstream side) of the gas phase reaction chamber 115 in order to stably perform a gas phase treatment in an atmosphere having a more constant concentration. It is preferable to install. In consideration of confidentiality in the gas phase treatment tank, the water seal unit 116 may be installed only on one of the inlet 115in side and the outlet 115out side, but is preferably installed at least on the outlet side, and installed on both sides. More preferably. However, when the water seal unit 116 is installed on the inlet 115in side, the fastener chain 120 is wetted, so that color unevenness is likely to occur during color tone processing by gas phase oxidation. For this reason, it is preferable not to install the water seal unit 116 on the inlet 115in side from the viewpoint of preventing uneven color. In this case, when the gas phase reaction chamber 115 is maintained at a negative pressure, air enters the gas phase reaction chamber 115. For this reason, it is also possible to supply air without going through the gas pipe 114b, and it is also possible to supply air together with the air from the gas pipe 114b.

On the other hand, it is advantageous in terms of safety management that it can be sealed in an emergency. For this reason, in the first embodiment, the water seal units 116 are installed on both the inlet 115in side and the outlet side, but during normal operation, only the outlet 115out side is sealed and the inlet 115in side is sealed. Not.

The vapor phase oxidation apparatus 110 preferably includes an air flow control mechanism that controls the gas phase oxidation gas supplied into the gas phase reaction chamber 115 to flow from the inlet 115in side to the outlet 115out side. Having such an airflow control mechanism is that the water seal unit 116 on the outlet 115out side is used for water sealing, while the water seal unit 116 is not installed on the inlet 115in side. This is particularly effective from the viewpoint of preventing gas leakage when not used for water sealing. On the other hand, the third embodiment to be described later is applicable, but the water seal unit 116 on the inlet 115in side is used for water sealing, and the water sealing unit 116 is not installed on the outlet 115out side or even if it is installed. When not used, it is preferable to control the gas-phase oxidizing gas supplied into the gas-phase reaction chamber 115 to flow from the outlet 115out side to the inlet 115in side.

Although there is no particular limitation on the airflow control mechanism, in the first embodiment, the airflow control mechanism includes at least one discharge port 114c for supplying gas for oxidizing gas phase installed in the gas phase reaction chamber 115, At least one suction port 121 for discharging the gas in the chamber 115 to the outside of the chamber 115 is provided. The suction port closest to the outlet side among the at least one suction port 121 is arranged on the outlet 115out side with respect to any of the at least one discharge port 114c, so that the gas supplied into the gas phase reaction chamber 115 is supplied. The phase oxidizing gas flows from the inlet 115in side to the outlet 115out side. In a preferred embodiment, all of the at least one suction port 121 is disposed on the outlet 115out side with respect to any of the at least one discharge port 114c. Then, by making the total gas suction amount from at least one suction port 121 larger than the total gas discharge amount from at least one discharge port 114c, the inside of the gas phase reaction chamber 115 becomes negative pressure and gas leakage is prevented. Can be prevented.

By passing the water seal unit 116 (exit) and the fastener chain 120 being discharged from the gas phase reaction chamber 115, the fastener chain 120 can be discharged while blocking the gas in the gas phase reaction chamber 115 from the outside. Further, an NH ₃ sensor (not shown) may be installed on the outside air side of the vapor phase oxidation apparatus 110. When NH ₃ flows out, an NH ₃ sensor (not shown) senses it, and the supply of NH ₃ can be stopped by a command from the control device 118.

Further, the control device 118 can control the flow rate of the gas-phase oxidizing gas supplied from the gas-phase oxidizing

gas storage units

114a and 114d through the discharge port 114c into the gas-phase reaction chamber 115. The gas concentration in the chamber 115 can be controlled. The gas-phase oxidizer 110 can be installed in a constant temperature and humidity control box, so that air whose temperature and humidity are controlled can be introduced into the gas-phase oxidizer 110. The temperature in the gas phase reaction chamber 115 can be controlled by a heating unit (not shown).

The fastener chain 120 passes through a water seal unit (upstream) 116 (not sealed during normal operation, but sealed only in an emergency) while being transferred by the transport mechanism 122. When entering, the gas-phase oxidizing gas supplied into the gas-phase reaction chamber 115 reacts with the copper alloy constituting the element surface of the fastener chain 120 that has been appropriately pretreated, and changes its color tone by the reaction mechanism described above. . Thereafter, the fastener chain 120 is discharged from the vapor phase oxidation apparatus 110 through the water seal unit (downstream) 116 while being transferred by the transport mechanism 122. Since the unreacted gas adhering to the fastener chain 120 passes through the water seal unit (downstream) 116 and is immersed in water, it is washed away.

<2-3-2 Second Embodiment>
FIG. 6 schematically shows a front view of the vapor phase oxidation apparatus 210 according to the second embodiment. The reference numerals in FIG. 6 have the same meaning as the reference numerals described in the first embodiment unless otherwise specified, and thus the description thereof is omitted. The vapor phase oxidation apparatus 210 according to the second embodiment is an embodiment effective in reducing the installation area. This embodiment can be said to be particularly advantageous when the installation space in the plane direction is small. In addition, although a control apparatus exists also in 2nd embodiment, illustration is abbreviate | omitted.

In the second embodiment, the gas phase reaction chamber 115 includes a first chamber 115a on the inlet side, a second chamber 115b on the outlet side, and a third chamber 115c between the first chamber 115a and the second chamber 115b. Prepare. The transport mechanism 122 is configured so that the article can sequentially pass through the first chamber 115a, the third chamber 115c, and the second chamber 115b, and the direction in which the fastener chain 120 passes through the third chamber 115c is vertical. The guide roller 122a can be included so as to include one or both of the upward direction and the downward vertical direction. The fastener chain 120 is transported by a drive source 122b installed outside the downstream side of the vapor phase oxidation apparatus 210.

When the transport distance of the fastener chain 120 when passing through the gas phase reaction chamber 115 is set to the same condition, a vertical upward direction and / or a vertical downward direction exist as directions in which the fastener chain 120 is transported, so that the horizontal direction is reached. The transport distance is shortened, which makes it possible to reduce the installation area of the vapor phase oxidation apparatus 210.

In the second embodiment, the third chamber 115c includes a third chamber upper portion 115c1 that is the same height as the first chamber 115a and the second chamber 115b, and a third chamber lower portion 115c2 that is below the third chamber upper portion. The transport mechanism 122 is configured such that the fastener chain 120 can pass through the first chamber 115a, the third chamber upper portion 115c1, the third chamber lower portion 115c2, and the second chamber 115b.

In the second embodiment, the fastener chain 120 passes through the first chamber in the horizontal direction and then enters the third chamber 115c. The fastener chain 120 reciprocates the third chamber upper portion 115c1 and the third chamber lower portion 115c2 in the third chamber 115c a plurality of times while moving in the vertical direction (in the second embodiment, the number of reciprocations is two times), and then the second chamber. 115b, and then passes through the water seal unit 116 on the outlet side and is discharged from the vapor phase oxidizer 210.

The installation area of the vapor phase oxidation apparatus 210 can be reduced as the ratio of the conveyance distance in the vertical direction in the third chamber 115c is increased. From the viewpoint of saving installation space, the total transport distance d1 in the vertical direction of the fastener chain 120 in the third chamber 115c is the total transport distance d2 in the horizontal direction in the first chamber 115a and the second chamber 115b. Longer, more preferably d1 / d ≧ 2, more preferably d1 / d2 ≧ 3, and even more preferably d1 / d2 ≧ 4. There is no particular upper limit for d1 / d2, but it is normal that d1 / d2 ≦ 20, and typically d1 / d2 ≦ 10.

The guide roller 122 installed in the third chamber lower part 115c2 can be a dancer roller. By moving the dancer roller up and down, it can be used as means for adjusting the tension on the conveyed fastener chain 120. It is also possible to adjust the distance that the fastener chain 120 passes through the gas phase reaction chamber 115 by changing the vertical installation location of the dancer roller according to the type of the fastener chain 120. As a result, the processing time can be changed without changing the conveying speed of the fastener chain 120, and there is also an advantage that it is easy to give a change in the color shade.

It is preferable that at least one gas-phase oxidizing gas discharge port 114c is provided in the third chamber lower portion 115c2, and the gas phase is located at a position lower than the lowest point through which the fastener chain 120 passes in the third chamber lower portion 115c2. More preferably, at least one oxidizing gas outlet 114c is provided. Thereby, the uniformity of the concentration of the gas for gas phase oxidation in the third chamber lower portion 115c2 can be improved.

Since the gas-phase oxidizing gas flows into the third chamber 115c, the concentration of the gas-phase oxidizing gas in the third chamber 115c tends to be higher than that of the first chamber 115a and the second chamber 115b. Since the third chamber 115c is disposed between the first chamber 115a and the second chamber 115b, the risk of the gas-phase oxidation gas leaking outside the device is reduced, and the safety of the gas-phase oxidation device 210 is reduced. It is increasing.

In the second embodiment, the water seal unit 116 is installed only on the outlet side. Therefore, from the viewpoint of preventing gas leakage, the vapor phase oxidation apparatus 210 preferably includes at least one suction port 121 in the second chamber 115b on the outlet side, and the suction port 121 is provided only in the second chamber 115b. More preferably. In the second embodiment, the gas-phase oxidation gas flowing into the third chamber lower portion 115c2 moves to the third chamber upper portion 115c1, and at least a part of the gas is used for the oxidation reaction of the fastener chain and passes through the second chamber 115b. And discharged from the suction port 121.

In the case of the first embodiment described above, when ammonia is used as the gas phase reaction gas, for example, ammonia is lighter than air, so it tends to move upward, and a concentration distribution may occur in the reaction chamber 115. For this reason, there is a possibility that color tone uniformity is impaired in the vertical direction of the fastener chain 120. On the other hand, in the case of the second embodiment, since the fastener chain 120 is transported in the vertical direction (vertical direction) in the third chamber lower portion 115c2, the concentration distribution of the gas phase reaction gas is generated in the vertical direction. Even so, the influence on the color uniformity of the fastener chain 120 in the vertical direction is suppressed. Therefore, the second embodiment is also advantageous in that the color tone uniformity on the front and back of the fastener chain 120 can be enhanced.

<2-3-3 Third Embodiment>
FIG. 7 schematically shows a front view of the vapor phase oxidation apparatus 310 according to the third embodiment. Unless otherwise specified, the reference numerals in FIG. 7 have the same meaning as the reference numerals described in the first embodiment, and thus the description thereof is omitted. The third embodiment differs from the first embodiment in that in the third embodiment, the water seal unit 116 on the outlet side is not used for water sealing during normal operation, and only the water seal unit 116 on the inlet side is used for water sealing. It is a point to be done. According to this embodiment, since the fastener chain 120 gets wet immediately before being subjected to gas phase oxidation, the fastener chain 120 after the color tone treatment is likely to have uneven color. However, when the uneven color is allowed or a design with uneven color is desired. This is a preferred embodiment.

In the third embodiment, since the installation location of the water seal unit 116 is changed to the inlet 115in side of the gas phase reaction chamber 115, the gas phase oxidation apparatus 310 supplies the gas phase oxidation gas supplied into the gas phase reaction chamber 115. It is preferable to provide an airflow control mechanism that controls the air flow from the outlet side to the inlet side. The provision of such an airflow control mechanism means that the water seal unit 116 on the inlet side is used for water sealing, while the water seal unit 116 on the outlet side is not installed or is installed. It is effective from the viewpoint of preventing gas leakage when not used for water sealing. Although there is no particular limitation on the airflow control mechanism, in the third embodiment, the airflow control mechanism includes at least one discharge port 114c for supplying a gas-phase oxidizing gas installed in the gas-phase reaction chamber 115; At least one suction port 121 for discharging the gas in the chamber 115 to the outside of the chamber 115 is provided. The suction port closest to the inlet 115in among the at least one suction port 121 is disposed in the inlet 115in side of any of the at least one discharge port 114c, and thus is supplied into the gas phase reaction chamber 115. The gas-phase oxidizing gas flows from the outlet 115out side to the inlet 115in side. In a preferred embodiment, all of the at least one suction port 121 is disposed closer to the inlet 115in than any of the at least one discharge port 114c. Then, by making the total gas suction amount from at least one suction port 121 larger than the total gas discharge amount from at least one discharge port 114c, the inside of the gas phase reaction chamber 115 becomes negative pressure and gas leakage is prevented. Can be prevented.

With this configuration, the gas in the gas phase reaction chamber 115 is sucked out of the gas phase reaction chamber 115 by being sucked out by the gas suction device 113 such as a blower from the suction port 121 installed in the vicinity of the inlet 115in of the gas phase reaction chamber 115. To be discharged.

(2-4 Color tone processing system)
FIG. 8 shows a configuration example of the color tone processing system 30 for continuously performing the pretreatment, the gas phase oxidation, and the rust prevention treatment described so far. The color tone treatment system 30 includes a degreasing device 31, a water washing device 32, a gas phase oxidation device 34, a water washing device 35, a rust prevention treatment device 36, a drying device 37, a surface treatment device 38, and a drying device 39 arranged in this order. A long slide fastener part 41 such as a chain is subjected to a predetermined process by sequentially passing through these apparatuses while being conveyed in a reel-to-reel manner in the direction of the arrow, and a color tone process is performed. The surface treatment device 38 can perform surface treatment such as clear lacquer coating and waxing.

Examples of the present invention will be described below, but these are provided for better understanding of the present invention and its advantages, and are not intended to limit the present invention.

(Test Example 1)
A metal fastener chain having a length of 200 to 250 mm after degreasing and washing was prepared. The element row of the metal fastener chain is made of a copper zinc alloy (Cu: 85 mass% (85.4 at.%), Zn: 15 mass% (14.6 at.%)). In addition, the said composition is a value when an unavoidable impurity is not considered, and an unavoidable impurity may be included in the composition of an element. The same applies to the following test examples. The element array is formed by pressing a Y-shaped bar after annealing into an element shape in a reducing atmosphere, and is crimped and fixed to a fastener tape.

The fastener chain is set in a gas phase reaction tubular furnace batch processing apparatus (φ75 mm quartz tube (0.6 L capacity)), and gas phase oxidation is performed using a mixed gas of air and ammonia gas under the reaction conditions shown in Table 1. It was. After the gas phase oxidation, it was washed with 2 L of water, then immersed in an aqueous benzotriazole solution for 1 minute for antirust treatment, and then washed with water and dried naturally. Neither clear lacquering nor waxing was performed.

(Test Example 2)
A metal fastener chain having a length of 200 to 250 mm after degreasing and washing was prepared. The element row of the metal fastener chain is made of a copper zinc alloy (Cu: 65 mass% (65.7 at.%), Zn: 35 mass% (34.3 at.%)). The element row is formed by pressing a Y-shaped bar after annealing in an oxidizing atmosphere into an element shape, and is fastened and fixed to a fastener tape. The fastener chain is set in a gas phase reaction tubular furnace batch processing apparatus (φ75 mm quartz tube (0.6 L capacity)), and gas phase oxidation is performed using a mixed gas of air and ammonia gas under the reaction conditions shown in Table 1. It was. The same antirust treatment as in Test Example 1 was performed on the fastener chain after the gas phase oxidation. Neither clear lacquering nor waxing was performed.

(Test Example 3)
A metal fastener chain having a length of 200 to 250 mm after degreasing and washing was prepared. The element row of the metal fastener chain is made of a copper zinc alloy (Cu: 60% by mass (60.7 at.%), Zn: 40% by mass (39.3 at.%)). The element row is formed by pressing a Y-shaped bar after annealing in an oxidizing atmosphere into an element shape, and is fastened and fixed to a fastener tape. The fastener chain is set in a gas phase reaction tubular furnace batch processing apparatus (φ75 mm quartz tube (0.6 L capacity)), and gas phase oxidation is performed using a mixed gas of air and ammonia gas under the reaction conditions shown in Table 1. It was. The same antirust treatment as in Test Example 1 was performed on the fastener chain after the gas phase oxidation. Neither clear lacquering nor waxing was performed.

(Test Example 4)
The same fastener chain as in Test Example 1 was colored by chemical conversion treatment using a liquid phase instead of vapor phase oxidation. Specifically, the chemical conversion treatment was performed by immersing the fastener chain after the degreasing water washing in the chemical conversion treatment liquid. After the chemical conversion treatment, the same rust prevention treatment as in Test Example 1 was performed. Neither clear lacquering nor waxing was performed.

(Test Example 5)
The same fastener chain as in Test Example 2 was colored by chemical conversion treatment using a liquid phase instead of vapor phase oxidation. Specifically, the chemical conversion treatment was performed by immersing the fastener chain after the degreasing water washing in the chemical conversion treatment liquid. After the chemical conversion treatment, the same rust prevention treatment as in Test Example 1 was performed. Neither clear lacquering nor waxing was performed.

(Test Example 6)
The same fastener chain as in Test Example 3 was colored by chemical conversion treatment using a liquid phase instead of vapor phase oxidation. Specifically, the chemical conversion treatment was performed by immersing the fastener chain after the degreasing water washing in the chemical conversion treatment liquid. After the chemical conversion treatment, the same rust prevention treatment as in Test Example 1 was performed. Neither clear lacquering nor waxing was performed.

For Test Examples 1 to 6, the obtained color tone changes depending on the processing time and the concentration of the gas or liquid to be processed, but changes from yellow to reddish brown to brown to dark brown depending on the time and concentration. Also, the estimated oxide film composition at that time is oxidized copper such as Cu ₂ O and CuO.

<Various performance tests>
Table 1 shows the results of the performance evaluation of the mechanical properties of the samples of the metal fastener chains of Test Examples 1 to 6.
“English class L” refers to a test (reciprocation durability test) according to the method of JIS S 3015: 2007. All samples gave a rating of “500 clears”. “500 times clear” means that there is no problem if the slider functions as a slide fastener even after the slider has been reciprocated 500 times with the fastener chain attached to the fastener chain. means.

“Friction fastness” was tested on the element by the method of JIS L 0803: 2011 and JIS L 0849: 2013, which are tests for dyeing tape. The fastness to friction was evaluated by the presence or absence of dirt (caused by adhesion and peeling) when the surface of the element after the test and the surface where the test cloth contacted was visually observed.
No dirt: ○
Dirty: ×

<Depth direction analysis of oxide layer>
For each sample of the metal fastener chains of Test Examples 1 to 6, the element surface after the gas phase oxidation or chemical conversion treatment and before the rust prevention treatment was subjected to AES analysis using an Auger electron spectrometer equipped with an FE electron gun. To obtain a depth profile. The AES analysis conditions were an electron gun acceleration voltage of 10 kV, a current amount of 3 × 10 ⁻⁸ A, a beam diameter of 50 μm, and a sample tilt of 30 °. For etching, an Ar monomer ion gun of 2 kV was used. The detection depth was calculated by converting from the sputtering time using the etching rate of 8.0 nm / min of the SiO ₂ standard material. The etching rate is a value obtained by dividing 100 nm by the time when the intensity of O of the SiO ₂ standard material (100 nm thermal oxide film on the Si substrate) becomes half.
The atomic concentrations of Cu, Zn, and O were calculated with relative sensitivity coefficients of Cu: 1, Zn: 1, and O: 1. The average Zn concentration, the average Cu concentration and the average O concentration in the oxide layer use the average of each measured value at a depth of 10 to 20 nm from the surface of the oxide layer, and the average Zn concentration and the average Cu concentration on the substrate surface are O Concentration 5 at. The average of measured values from the boundary between the oxide layer and the base material (base material surface) of 20% or less to a depth of 20 nm was used. For reference, depth profiles of Test Examples 3 and 6 are shown in FIGS.

* 1: Ammonia concentration: 100% ammonia gas Vol / (air + 100% ammonia gas) Vol x 100

From the results shown in Table 1, the results of the test examples 1 to 3 with respect to the British L class test are the same as those of the conventional chemical conversion treatment (Test Examples 4 to 6). This sample was superior to Test Examples 4-6.

<Oxidation layer depth analysis for samples with finishing layer>
Each sample of the metal fastener chains of Test Examples 1 to 3 described above was subjected to rust prevention treatment and clear lacquer coating in order after vapor phase oxidation. Remove the clear lacquer and rust preventive treatment layer by exposing the dried sample (Esback H-300 manufactured by Sasaki Chemicals) to room temperature overnight by removing the clear lacquer and the anti-rust treatment layer from each sample after drying. did. Next, when the depth direction analysis of the oxide layer was performed by the method described above, substantially the same test results as before the finish layer were formed were obtained for any sample.

10, 20 Article 11 Base 12 Oxidation layer 13

Finishing layer

110, 210, 310 Gas phase oxidation device 118 Control device 112 Ammonia gas decomposition device 113 Blower (gas suction device)
114 Gas supply system for gas phase oxidation 115 Gas phase reaction chamber 116 Water seal unit 120 Fastener chain 122 Conveying mechanism 30 Color tone processing system 31 Degreasing device 32 Water washing device 34 Gas phase oxidation device 35 Water washing device 36 Rust prevention processing device 37 Drying device 38 Surface treatment device 39 Drying device 41 Slide fastener parts

Claims

The substrate 11 has at least a surface made of a copper alloy containing zinc, and an oxide layer 12 adjacent to the surface of the substrate 11, and has a depth of 10 nm with respect to the surface of the oxide layer 12. Articles in which the ratio A of the average zinc concentration to the average copper concentration in the range up to a depth of 20 nm is higher than the ratio B of the average zinc concentration to the average copper concentration on the surface of the substrate 11.
The average zinc concentration on the surface of the substrate 11 is 5 to 50 at. The article of claim 1, which is%.
The article according to claim 1 or 2, wherein the ratio A / B of the ratio A to the ratio B is 2.0 or more.
The article according to any one of claims 1 to 3, wherein the entire substrate 11 is made of a copper alloy containing zinc.
The average zinc concentration in the range from a depth of 10 nm to a depth of 20 nm with respect to the surface of the oxide layer 12 is 5 to 80 at. The article of claim 4, which is%.
The article according to any one of claims 1 to 5, wherein the article is a slide fastener member.
A slide fastener comprising the article according to claim 6.
A method for color tone treatment of an article, comprising subjecting an article having a substrate composed of a copper alloy containing at least a surface of zinc to gas phase oxidation in the presence of at least oxygen.
An oxide layer adjacent to the substrate surface, wherein the ratio A of the average zinc concentration to the average copper concentration in the range from a depth of 10 nm to a depth of 20 nm with respect to the oxide layer surface is an average on the substrate surface The color tone processing method for an article according to claim 8, comprising forming an oxide layer having a higher ratio B of the average zinc concentration to the copper concentration by vapor phase oxidation.
The color tone processing method according to claim 8 or 9, wherein the gas phase oxidation is carried out in the presence of ammonia.
The color tone control by gas phase oxidation is selected from the group consisting of ammonia concentration, oxygen concentration, other reactive gas concentration, humidity in the reaction system, temperature in the reaction system, processing time, and article temperature. The color tone processing method according to any one of claims 8 to 10, which is performed by changing one or more of them.
The color tone processing method according to any one of claims 8 to 11, wherein the article is a fastener member.
The color tone processing method according to any one of claims 8 to 12, wherein the gas phase oxidation is performed at an atmospheric temperature of 20 to 80 ° C.
The color tone processing method according to any one of claims 8 to 13, wherein the gas phase oxidation is performed under a negative pressure.
The color tone processing method according to any one of claims 8 to 14, further comprising sequentially performing activation treatment and water washing on the surface of the substrate before performing the gas phase oxidation.
The color tone processing method according to any one of claims 8 to 15, further comprising sequentially performing degreasing and water washing on the surface of the base material before performing the gas phase oxidation.
15. The method according to claim 8, further comprising performing at least one surface treatment selected from the group consisting of clear coating, rust prevention treatment and waxing on the surface of the oxide layer formed by the gas phase oxidation. The color tone processing method according to Item.
A gas phase reaction chamber 115 for performing gas phase oxidation having an inlet 115in and an outlet 115out, and a long member having at least a part of which at least a surface is made of metal enter from the inlet and pass through the gas phase reaction chamber 115. Then, a transport mechanism 122 for continuously exiting from the outlet, a discharge port 114c for supplying a gas-phase oxidation gas into the gas-phase reaction chamber 115, and a gas-phase reaction chamber 115 A gas phase oxidation apparatus for carrying out a color tone processing method provided with a suction port 121 for discharging gas out of the chamber 115.
19. The water seal unit 116 for blocking a gas inside the gas phase reaction chamber 115 is installed on either or both of the outlet 115 out side and the inlet 115 in side of the gas phase reaction chamber 115. Gas phase oxidation equipment.
20. The gas phase oxidation apparatus according to claim 19, wherein a water seal unit 116 for blocking gas inside the gas phase reaction chamber 115 from the outside is installed only on the outlet 115out side of the gas phase reaction chamber 115.
21. The vapor phase oxidation apparatus according to claim 20, further comprising an airflow control mechanism for controlling the gas phase oxidation gas supplied into the gas phase reaction chamber 115 to flow from the inlet 115in side to the outlet 115out side.
The air flow control mechanism includes at least one discharge port 114c for supplying a gas-phase oxidizing gas installed in the gas-phase reaction chamber 115 and discharging the gas in the chamber 115 to the outside of the chamber 115. The at least one suction port 121 is provided, and all the suction ports of the at least one suction port 121 are arranged on the outlet side of all the discharge ports of the at least one discharge port. Gas phase oxidation equipment.
The gas phase according to claim 22, wherein the transport mechanism 122 is configured to include one or both of a substantially vertical upward direction and a substantially vertical downward direction as a direction in which the article passes through the gas phase reaction chamber 115. Oxidation equipment.
The gas phase reaction chamber 115 includes a first chamber 115a on the inlet 115in side, a second chamber 115b on the outlet 115out side, and a third chamber 115c between the first chamber 115a and the second chamber 115b, The transport mechanism 122 is configured so that the article can sequentially pass through the first chamber 115a, the third chamber 115c, and the second chamber 115b, and is substantially vertical as a direction in which the article passes through the third chamber 115c. 24. The gas phase oxidation apparatus according to claim 23, configured to include one or both of an upward direction and a substantially vertical downward direction.
The third chamber 115c includes a third chamber upper portion 115c1 and a third chamber lower portion 115c2 below the third chamber upper portion 115c1, which are at the same height as the first chamber 115a and the second chamber 115b. The gas phase oxidation apparatus according to claim 24, wherein the article is configured to be able to pass through the first chamber 115a, the third chamber upper part 115c1, the third chamber lower part 115c2, and the second chamber 115b.
The vapor phase oxidation apparatus according to claim 24 or 25, wherein the third chamber lower portion 115c2 includes at least one discharge port 114c, and the second chamber 115b includes at least one suction port 121.
27. The transfer mechanism 122 is configured to include both a substantially vertical upward direction and a substantially vertical downward direction as directions in which the article passes through the third chamber 115c. The gas phase oxidation apparatus as described.