TWI666342B - Object and its color processing method, zipper and gas phase oxidation device - Google Patents

Abstract

The present invention improves the fastness to rubbing after an object having a base material containing at least a surface of a copper-zinc alloy is subjected to hue treatment. Moreover, this invention provides the apparatus which performs the color tone processing which can suppress the amount of water usage compared with a wet process. An object includes: a substrate 11 including at least a copper alloy containing zinc on its surface; and an oxide layer 12 adjacent to the surface of the substrate 11 and based on the surface of the oxide layer 12 from a depth of 10 nm to a depth of 20 nm The ratio A of the average zinc concentration to the average copper concentration in the range above is higher than the ratio B of the average zinc concentration to the average copper concentration on the surface of the substrate 11.

Description

Object and its color processing method, zipper and gas phase oxidation device

The present invention relates to an object having a metal surface, and more particularly to a metal fastener component. In addition, the present invention relates to a color tone processing method for an object having a metal surface, and more particularly, to a color tone processing method for a metal fastener member. Furthermore, this invention relates to the gas-phase oxidation apparatus which implements the color tone processing method of the long object which has a metal surface.

Among the fasteners, there are products of a type called metal fasteners that are composed of metal (such as gunmetal), brass, zinc-plated copper, and aluminum, and are made of metal elements. Among them, bronze, brass, and other metals are used. Copper-zinc alloy metal fasteners, such as zinc white copper, are used in large quantities because they have a good balance of price, strength, hardness, and processability. In the field of fashion dealing in clothes or apparel, not only are the fasteners required to have excellent functionality, but also the designability of designs suitable for objects. Therefore, in metal fasteners, it is also required to provide metal fastener members having a variety of colors so as to be able to cope with patterns of various objects.

Previously, there were methods for treating the color tone of a metal surface: a method of surface coating with an organic paint or the like; a method of changing color tone by changing the composition or plating a metal with a different composition on the surface ; And a method of coloring the surface to a specific color by performing a certain chemical conversion treatment on the metal surface, etc., but the mainstream is to perform color tone processing by wet processing.

For example, Japanese Patent Application Laid-Open No. 2014-205871 (Patent Document 1) describes a treatment method in which the appearance of the surface is colored to a blue hue by immersion treatment in a chlorite-based chemical conversion treatment liquid. Specifically, there is described a blue coloring method for a copper-based metal surface, which is characterized in that it contains 0.5 g / L to 250 g / L of chlorite and 1 g / L to 625 g / L of an alkali metal. The chlorite-based chemical conversion treatment solution of the hydroxide is subjected to immersion treatment of the copper-based metal. In the Example, the operation described below is performed after copper-plating a button upper mold member made of brass, and performing a chemical conversion treatment.

[Prior Art Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2014-205871

When 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 research results of the present inventors, it has been found that when the chemical conversion treatment is performed on a copper-zinc alloy object, a problem that the fastness to rubbing is reduced occurs. In terms of providing a wide range of copper-zinc alloy objects, it is desirable to adjust the copper-zinc alloy objects to various shades without sacrificing rubbing fastness.

Therefore, one of the problems of the present invention is to improve the rubbing fastness after subjecting an object having a substrate containing at least its surface to a copper-zinc alloy to a color tone treatment.

In addition, when the color tone processing is performed by wet processing, use A large number of chemicals cause various problems such as an increase in the load on drainage treatment, difficulty in implementation in areas where water resources are scarce, and the parts of the hue treatment device are easily corroded by chemicals.

Therefore, another object of the present invention is to provide an apparatus for performing a hue treatment capable of reducing a drainage load as compared with a wet process.

The inventors performed a color tone treatment by chemically treating the surface of a copper-zinc alloy by the method described in Patent Document 1, and then observed a cross section near the surface of the copper-zinc alloy with an electron microscope. As a result, it was found that the section Porous structure with voids visible everywhere. It is presumed to: a porous structure caused by the following results: by chemical conversion treatment near the surface cause the following chemical _{^{reaction: Zn + 2OH - + 2H 2}} O → [Zn (OH) 4] 2-, whereby dezincification.

Based on the inference, the present inventors have worked hard on the surface structure of copper-zinc alloy objects with changed hue to improve the fastness to rubbing and found that it is effective to solve The dense oxide layer in which zinc is concentrated has a function of changing color tone.

The present invention has been completed based on the above-mentioned findings, and an aspect of the present invention is an object including: a substrate, at least a surface of which includes a copper alloy containing zinc; and an oxide layer, which is adjacent to the surface of the substrate, and 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 based on the surface of the oxide layer is higher than the ratio of the average zinc concentration to the average copper concentration in the surface of the substrate B.

In one embodiment of the object of the present invention, the average zinc concentration on the surface of the substrate is 5 at.% To 50 at.%.

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

In still another embodiment of the object of the present invention, the entire substrate includes a copper alloy containing zinc.

In still another embodiment of the object of the present invention, an average zinc concentration in a range from a depth of 10 nm to a depth of 20 nm based on the surface of the oxide layer is 5 at.% To 80 at.%.

In still another embodiment of the object of the present invention, the object is a zipper member.

Another aspect of the present invention is a zipper including the zipper member of the present invention.

Yet another aspect of the present invention is a method for processing an object's hue, which includes subjecting an object having a substrate including at least a surface of a copper alloy containing zinc to vapor phase oxidation in the presence of at least oxygen.

In one embodiment of the color tone processing method of the object of the present invention, the method includes forming an oxide layer by gas phase oxidation, the oxide layer is adjacent to the surface of the substrate, and the surface of the oxide layer is used as a reference from a depth of 10 nm to The ratio A of the average zinc concentration to the average copper concentration in a range up to a depth of 20 nm is higher than the ratio B of the average zinc concentration to the average copper concentration in the surface of the substrate.

In another embodiment of the color tone processing method for an object of the present invention, Gas phase oxidation is performed in the presence of ammonia.

In still another embodiment of the color tone processing method of the object of the present invention, the method 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, and processing. One or more of the groups consisting of time and temperature of the object are changed to perform the hue control of the gas-phase oxidation.

In still another embodiment of the color tone processing method for an object according to the present invention, the object is a fastener member.

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

In still another embodiment of the color tone processing method of the object of the present invention, the gas-phase oxidation is performed under a negative pressure.

In still another embodiment of the method for processing a color tone of an object of the present invention, before performing the vapor-phase oxidation, the substrate surface is sequentially subjected to activation treatment and water washing.

In still another embodiment of the method for processing a color tone of an object of the present invention, the surface of the substrate is sequentially degreased and washed with water before the gas phase oxidation is performed.

In still another embodiment of the color tone processing method of the object of the present invention, the surface of the oxide layer formed by the gas-phase oxidation is subjected to a process selected from the group consisting of a clear coating, an antirust treatment, and a wax coating. At least one or more surface treatments in the group.

Yet another aspect of the present invention is a gas phase oxidation device for implementing a color tone processing method, which includes: a gas phase reaction chamber having an inlet and an outlet for performing gas phase oxidation; and a transfer mechanism for at least a part of A long member having a portion containing at least a surface of a metal enters from the inlet, passes through the gas-phase reaction chamber, and is continuously sent out from the outlet; a spray outlet is used to supply gas-phase oxidation gas to the gas-phase reaction A chamber; and a suction port for exhausting the gas in the gas-phase reaction chamber to the outside of the chamber.

In one embodiment of the gas-phase oxidation device of the present invention, a water seal for blocking the gas inside the gas-phase reaction chamber is provided on one or both of the outlet side and the inlet side of the gas-phase reaction chamber. unit.

In another embodiment of the gas-phase oxidation device of the present invention, a water-sealing unit is provided only at the outlet side of the gas-phase reaction chamber to block the gas inside the gas-phase reaction chamber from the outside.

In still another embodiment of the gas-phase oxidation device according to the present invention, a gas-flow control mechanism is provided to flow the gas-phase oxidation gas supplied into the gas-phase reaction chamber from the inlet side to the outlet. Side control.

In still another embodiment of the gas-phase oxidation device of the present invention, the gas flow control mechanism includes at least one ejection port provided in the gas-phase reaction chamber for supplying gas for gas-phase oxidation, and for The gas in the chamber is exhausted to at least one suction port outside the chamber, and all the suction ports in the at least one suction port are arranged closer to the outlet side than all the discharge ports in the at least one discharge port.

In still another embodiment of the gas-phase oxidation device of the present invention, the The transfer mechanism 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 object passes through the gas phase reaction chamber.

In still another embodiment of the gas-phase oxidation device 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 third chamber on the side Between the first chamber and the second chamber, the transfer mechanism is configured to allow the object to pass through the first chamber, the third chamber, and the second chamber in this order, and is configured to include a substantially vertical upward direction. One or both of the substantially vertical down direction is a direction in which the object passes through the third chamber.

In still another embodiment of the gas-phase oxidation device of the present invention, the third chamber includes: an upper portion of the third chamber, which is located at the same height as the first chamber and the second chamber; and a lower portion of the third chamber, which is located Further to the lower side than the upper part of the third chamber, the transfer mechanism is configured to allow the object to pass through the first chamber, the upper part of the third chamber, the lower part of the third chamber, and the second chamber.

In still another embodiment of the gas-phase oxidation device of the present invention, at least one of the ejection ports is provided in a lower portion of the third chamber, and at least one of the suction ports is provided in a second chamber.

In still another embodiment of the gas-phase oxidation device of the present invention, the transfer mechanism is configured to include both a substantially vertical upward direction and a substantially vertical downward direction as a direction in which the object passes through the third chamber.

According to the present invention, in an object made of a copper-zinc alloy, the surface whose color tone is changed can improve the rubbing fastness. Especially considering metal fastening In terms of component members, rubbing fastness is an important characteristic, and it is of great commercial significance to impart a hue change to a copper-zinc alloy fastener member without sacrificing rubbing fastness. In addition, according to the present invention, it is possible to easily change an object having a copper-zinc alloy on the surface into various color tones by changing the type and ratio of oxides constituting the oxide layer. In addition, in the object of the present invention, since Zn remains near the surface, there is also an advantage that the hue can be changed using Zn. That is, in the conventional chemical treatment, zinc is dezincified near the surface, so elements Cu and O participating in hue change become the main body. According to the present invention, zinc remains on the surface. Therefore, in addition to Cu and O, Zn can also participate in hue change. The result is a variety of shades. Therefore, the present invention is also advantageous in that various product expansions can be performed. In addition, the gas-phase oxidation device of the present invention basically does not need to use water in the reaction chamber.

10, 20‧‧‧ objects

11‧‧‧ Substrate

12‧‧‧ oxide layer

13‧‧‧finished layer

30‧‧‧Hue Processing System

31‧‧‧Degreasing device

32, 35‧‧‧washing device

34‧‧‧Gas phase oxidation device

36‧‧‧Anti-rust treatment device

37, 39‧‧‧ drying device

38‧‧‧ surface treatment device

41‧‧‧Zipper parts

110, 210, 310‧‧‧‧Gas phase oxidation device

112‧‧‧Ammonia gas decomposition device

113‧‧‧blower (gas suction device)

114‧‧‧Gas supply system for gas phase oxidation

114a, 114d‧‧‧Gas storage unit

114b‧‧‧Gas piping

114c‧‧‧Ejection outlet (gas ejection outlet)

115‧‧‧ gas-phase reaction chamber

115a‧‧‧1st chamber

115b‧‧‧ 2nd chamber

115c‧‧‧3rd chamber

115c1‧‧‧3rd upper chamber

115c2‧‧‧3rd lower chamber

115in‧‧‧Entrance

115out‧‧‧Exit

116‧‧‧Water sealed unit

118‧‧‧Control

120‧‧‧Zipper chain

121‧‧‧ Attraction

122‧‧‧Transportation agency

122a‧‧‧Guide roller

122b‧‧‧Driver

123‧‧‧Piping

FIG. 1 is a diagram schematically showing an example of a cross-sectional structure of an object of the present invention.

FIG. 2 is a diagram schematically showing another example of a cross-sectional structure of an object of the present invention.

FIG. 3 is a graph showing a depth profile of atomic concentrations of O, Cu, and Zn when the sprocket surface of Test Example 3 is analyzed by Auger Electron Spectrometry (AES).

FIG. 4 is a graph showing a deep section of atomic concentrations of O, Cu, and Zn when AES analysis is performed on the surface of a sprocket in Test Example 6. FIG.

FIG. 5 is a schematic front view showing a first embodiment of the vapor phase oxidation device of the present invention.

Fig. 6 is a schematic front view showing a second embodiment of the vapor-phase oxidation device of the present invention.

FIG. 7 is a schematic front view showing a third embodiment of the vapor-phase oxidation device of the present invention.

FIG. 8 is a schematic front view showing a device configuration example of a tone processing system according to the present invention.

<1. Object>

In one embodiment, the object of the present invention has a substrate including at least a surface of a copper alloy containing zinc. As a copper alloy containing zinc, from the viewpoints of strength, cost, and processability, copper-zinc alloys such as brass, bronze, and zinc white copper, or copper-zinc-nickel alloys are excellent and can be preferably used. For example, a copper alloy containing zinc may be composed of 1 to 40% by mass, preferably 4 to 40% by mass of Zn, and 0 to 10% by mass selected from Ni and Be. Or more of Mo, Al, Sn, Pb, Mn, Fe, P, and S, and the remainder contains copper and unavoidable impurities. The base material may include a copper alloy containing at least zinc on the surface, and includes a case where a resin, ceramic, or the like is contained inside by a laminated structure. Of course, as for the base material, the whole including not only the surface but also the inside may contain a copper alloy containing zinc.

The object and type of the object of the present invention are not particularly limited, and may be a metal fastener member in a typical embodiment. Examples of the metal fasteners include a zipper, a daughter fastener, and the like. Examples of fields other than metal fasteners include ball chains. The member for a zipper is not limited, and a sprocket (card Components), sliders, pull tabs, upper stops, lower stops, and opening and closing inserts. Examples of the members for the female and female fasteners include male and female fasteners. The metal fastener member may be in the shape of the final part attached to the fastener product as described above, or may be in the form of a wire, a plate, a pipe, a rod, or the like before the shape processing.

FIG. 1 schematically illustrates a cross-sectional structure of an embodiment of an object of the present invention. The object 10 includes a substrate 11 and an oxide layer 12 adjacent to a surface of the substrate 11. In this 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 in the surface of the substrate 11. That is, zinc is concentrated in the oxide layer 12. This case means that dezincification does not occur in the oxide layer 12, and thereby the oxide layer 12 can be prevented from exhibiting a porous structure. The average zinc concentration and the average copper concentration of the oxide layer 12 are respectively expressed by the following average atomic concentration of Zn and average atomic concentration of Cu: by Auger electron spectrometry (AES), and by Ar ion etching, from the surface of the oxide layer Elemental composition analysis was performed in the depth direction, and the average atoms of Zn in a range from a depth of 10 nm to a depth of 20 nm based on the surface of the oxide layer when the total number of atoms of Cu, Zn, and O was 100%, based on the surface of the oxide layer. Concentration and average atomic concentration of Cu. In the present invention, the depth when performing composition analysis in the depth direction using AES refers to the depth when the etching rate is 8.0 nm / min using a SiO ₂ standard material, and conversion is performed based on the sputtering time (the same applies hereinafter). In addition, if the finishing layer 13 described later does not exist on the oxide layer 12, the oxide layer 12 becomes the outermost layer.

In a preferred embodiment of the object of the present invention, the ratio A / B of the ratio A in the oxide layer 12 to the ratio B in the surface of the substrate 11 is greater than 1.0, This ratio may also be set to 1.5 or more, and may also be set to 2.0 or more. For example, it may be set to 1.2 to 3.0.

In one embodiment of the object of the present invention, the average zinc concentration in the range from a depth of 10 nm to a depth of 20 nm is 5 at.% Or more based on the surface of the oxide layer 12. In a more typical embodiment, it is 10at.% Or more. In one embodiment of the object of the present invention, the average zinc concentration in the range from a depth of 10 nm to a depth of 20 nm is 80 at.% Or less based on the surface of the oxide layer 12. In a more typical embodiment, 60 at.% Or less, 40 at.% Or less in a still more typical embodiment, and 30 at.% Or less in a further more typical embodiment. The average zinc concentration of the oxidized layer 12 is expressed by the average atomic concentration of Zn. The composition analysis of the surface of the oxidized layer in the depth direction is performed by Auger Electron Spectroscopy (AES). The total atomic concentration of Zn was 100%.

In one embodiment of the object of the present invention, the average oxygen concentration in a range from a depth of 10 nm to a depth of 20 nm based on the surface of the oxide layer 12 is 20 at.% Or more, and in a typical embodiment, it is 20 at. .% ~ 60at.%, In a more typical implementation form, 30at.% ~ 50at.%. The average oxygen concentration of the oxidized layer 12 is expressed by the average atomic concentration of O. The composition analysis of the depth of the oxidized layer from the surface of the oxidized layer is performed by Auger Electron Spectroscopy (AES). The average atomic concentration of O when the total is 100%.

In the present invention, the boundary between the oxide layer and the substrate refers to the position where the composition analysis of Cu, Zn, and O from the surface of the oxide layer to the substrate in the depth direction is performed by the Auger electron spectrometry (AES). When the total number of atoms is set to 100%, The subconcentration initially reached a depth position below 5 at.%. Furthermore, there is a case where another layer (finished layer) is formed on the oxide layer, and the definition of the surface of the oxide layer (the boundary between the other layer and the oxide layer) in this case will be described later.

For reasons of improving the strength, the average zinc concentration in the surface of the substrate is preferably 5 at.% Or more, and more preferably 10 at.% Or more. In addition, for reasons of improving workability, the average zinc concentration in the surface of the substrate is preferably 50 at.% Or less, and more preferably 40 at.% Or less. The average zinc concentration and average copper concentration in the surface of the substrate are respectively expressed by the following average atomic concentration of Zn and average atomic concentration of Cu: from the surface of the substrate to a depth of 20 nm by the Auger electron spectrometry (AES) The composition analysis was performed in the depth direction, and the average atomic concentration of Zn and the average atomic concentration of Cu from the surface of the substrate to the depth when the total number of atoms of Cu, Zn, and O was 100% were set to the depth.

When the entire substrate includes a copper alloy containing zinc, the average zinc concentration in the entire substrate is also preferably 5 at.% Or more, and more preferably 10 at.% Or more, for reasons of improving the strength. In addition, for reasons of improving processability, the average zinc concentration in the entire substrate is preferably 50 at.% Or less, and more preferably 40 at.% Or less. The average zinc concentration in the entire substrate is expressed by the atomic concentration of Zn when the total number of atoms of Cu, Zn, and O in the entire substrate is 100%, and it can be analyzed by a fluorescent X-ray analyzer .

FIG. 2 schematically illustrates a cross-sectional structure of another embodiment of the object of the present invention. The object 20 includes a substrate 11, an oxide layer 12 adjacent to the surface of the substrate 11, and a finishing layer 13 adjacent to the surface of the oxide layer 12. This embodiment and figure The difference of the first embodiment lies 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 two or more surface treatment agents such as clear lacquer, rust inhibitor, and wax. The surface treatment agents may be used alone or in combination of two or more. In addition, the finishing layer may be a single layer or a plurality of layers.

The drug for the transparent lacquer coating is not particularly limited, and examples thereof include one selected from the group consisting of acrylic resin, polyester resin, alkyd resin, urethane resin, and epoxy resin. Two or more types of resin components, one or two or more types of crosslinking agents and other additives selected from the group consisting of block polyisocyanate, melamine resin, and urea resin, and other additives are prepared by dissolving or dispersing them in organic solvents or water. There are no particular restrictions on the rust-preventing chemical, and examples thereof include benzotriazole-based, phosphate-based, and imidazole-based. The medicine for wax is not particularly limited, and usually paraffin may be used as a main component, and a conventional wax component may be added if necessary.

In the case where a 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 in the surface of the substrate 11 can be performed in the depth direction by one side of the finishing layer. AES analysis was performed while etching until the surface of the substrate was measured. In addition, when the thickness of the finishing layer is high, it can be measured by performing AES analysis in the depth direction similarly before and after removing the finishing layer to the oxide layer.

The finishing layer may be removed by a release agent as appropriate. As a peeling agent, for example, an object can be peeled by immersing an object in the trade name "S-BACK H-300" (made by Sasaki Chemicals) at room temperature for about one night. Furthermore, with the finishing layer The thickness of the release agent can be changed. However, if the oxide layer is removed except for the finishing layer, the boundary between the finishing layer and the oxide layer disappears. Therefore, it is desirable to remove the finishing layer to such an extent that a part of the finishing layer remains.

The boundary between the finishing layer and the oxide layer can be identified by changes in Cu and Zn concentrations. Cu and Zn were basically not detected in the finishing layer, but a large amount of Cu and Zn were detected in the oxide layer. Therefore, in this specification, a depth position where the total atomic concentration of Cu and Zn when the total atomic concentration of Cu and Zn reaches 1% or more when the AES analysis is performed in the depth direction is defined as the boundary between the finishing layer and the oxide layer. The atomic concentrations of Cu and Zn are represented by the ratio of the number of atoms of each of Cu and Zn to the total number of atoms of Cu, Zn, and O.

<2. Manufacturing method of object>

The object of the present invention can be produced, for example, by subjecting the surface of the substrate to gas phase oxidation. Gas-phase oxidation significantly reduces the problems of environmental load and drainage treatment costs caused by harmful substances, and further facilitates the change of oxidation reaction conditions. Therefore, it is advantageous in that a single device can be multicolored. Hereinafter, specific embodiments of the gas phase oxidation will be described in detail. The gas-phase oxidation may be performed on a separate member of the substrate, or on a state where the substrate is combined with other parts. For example, in a case where the base member is a fastener element of a zipper, a fastener stringer in which the fastener element rows of the zipper are attached to a fastener tape, or a fastener in which the fastener element rows of a pair of fastener chain members are engaged with each other The chains are subjected to gas phase oxidation.

(2-1 pre-processing)

It is preferred to perform a pretreatment before subjecting the surface of the substrate to vapor phase oxidation. The reason is that the reactivity improvement or uniformity of gas phase oxidation can be obtained according to the type of pretreatment. Improving effects. Specific examples of the pretreatment method include a metal activation treatment. By performing a metal activation treatment, the reaction efficiency at the time of gas-phase oxidation can be improved.

There are two methods of metal activation treatment: wet and dry.

Examples of the wet method include a method in which an acidic or alkaline aqueous solution is brought into contact with the surface of a substrate and treated. Examples of the acidic aqueous solution include aqueous solutions of inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, chromic acid, and phosphoric acid, and organic acids such as acetic acid and dibasic acids (oxalic acid, malonic acid, succinic acid, and aspartic acid). Water solution. Examples of the alkaline aqueous solution include aqueous ammonia, aqueous NaOH, sodium carbonate, and sodium silicate. Among these, in terms of removability of the oxidized film and the like after the treatment, the acidity is preferably hydrochloric acid, and the basicity is preferably an aqueous NaOH solution. The method for bringing an acidic or alkaline aqueous solution into contact with the surface of the substrate is not limited, and examples thereof include immersion of the substrate in the aqueous solution, spraying, dripping, coating, roll coating, and flow coating on the substrate. The aqueous solution and the like.

Examples of the dry method include a plasma treatment (for example, an oxygen (O ₂ ) plasma treatment), an ultraviolet (Ultra Violet) ozone method, a Malcomizing method, and a halogen-based gas treatment.

In the case of either the wet type or the dry type, in terms of removing residual components, it is desirable to perform water washing after the metal activation treatment.

In order to improve the effect of the pretreatment, it is preferable to perform a degreasing and a water washing treatment on the substrate before performing the pretreatment. The degreasing method may be any known method, and examples thereof include a method in which a degreasing agent is brought into contact with the surface of the substrate by dipping, wiping, brushing, spraying, or the like. In order to improve the degreasing effect during dipping, Shake or ultrasound can be applied. Furthermore, a conventional surface treatment such as a chemical polishing treatment, a metal plating treatment, a physical polishing treatment, and a pre-degreasing treatment may be performed before the deesterification and water washing treatments.

(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. Regarding the method of vapor phase oxidation, various methods can be considered. For example, when copper and zinc are oxidized in the presence of oxygen, they can be changed into copper oxide and zinc oxide by a chemical reaction described below. By changing the conditions for gas-phase oxidation and the oxidation state of Cu and Zn on the surface of the substrate, various hue can be adjusted.

． Cu + 1 / 2O ₂ → Cu ₂ O (monovalent) → CuO (divalent)

． Zn + 1 / 2O ₂ → ZnO (divalent)

However, under low temperature conditions, the oxidation reaction is slow, so it is preferred to promote oxidation. In order to promote oxidation, the heating temperature can be increased. However, when the base material is combined with other materials with low heat resistance, for example, when the base material is a fastener element of a zipper, when gas phase oxidation is performed in the state of a zipper chain, there is a need to The heat-resistant temperature of synthetic fiber-made fastener tapes and the like is limited to a certain level. Therefore, 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 processing method of the substrate of the present invention, the gas-phase oxidation is performed in the presence of oxygen and ammonia. As a supplier of oxygen The method is not particularly limited, and examples thereof include a method of supplying in the form of air, oxygen, a mixed gas of oxygen, and an inert gas (such as nitrogen or a rare gas). For reasons of cost, the method is preferably air Methods.

Ammonia is a cheap and universal gas available in countries around the world. Ammonia can be converted to nitrogen (N ₂ ) and hydrogen (H ₂ ), hydrogen by thermal decomposition (NH ₃ → 1 / 2N ₂ + 3 / 2H ₂ ). Furthermore, it can be converted into water (H ₂ → H ₂ O). Therefore, clean exhaust gas can be discharged. In addition, after gas-phase oxidation, the object is washed with water, whereby the ammonia-containing water that can be generated is neutralized and converted into ammonium sulfate (fertilizer raw material). As described above, ammonia is a substance that is highly economical and has a small environmental load.

The gas-phase oxidation can be performed, for example, at 0 ° C to 100 ° C, and can be performed even at room temperature. Therefore, it can be carried out without extra cooling cost or heating cost, but in order to promote the reaction, it is preferable to perform heating slightly. Therefore, the gas phase oxidation is preferably carried out at an ambient temperature of 20 ° C or higher, and more preferably carried out at an ambient temperature of 30 ° C or higher.

In addition, the gas-phase oxidation can be carried out under atmospheric pressure, and it is not necessary to carry out under reduced pressure or pressure. However, from the viewpoint of safety, it is preferable to set the reaction chamber to a negative pressure to prevent leakage of internal gas such as ammonia. Therefore, the gas-phase oxidation is preferably performed under reduced pressure (slightly negative pressure from atmospheric pressure).

It is not intended to limit the present invention by theory, but it is presumed that if moisture (H ₂ O) (wet state) is appropriately present on the surface of the substrate, NH _{3 is} ionized to NH ₄ ⁺ and NH ₄ ^{+ is} bonded to the fastener The metal (for example, Cu and Zn) on the surface of the member promotes the oxidation reaction. Taking the oxidation of Cu as an example, it is considered that the oxidation can be promoted by the rapid progress of the reaction described below. The hue is changed by the formation of metal oxides or 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

Furthermore, under the conditions of ammonia surplus, a reaction of the following formula was carried out, and it was colored blue.

． Cu (OH) ₂ + 4NH ₃ → [Cu (NH ₃ ) ₄ ] (OH) ₂

Furthermore, when strong hydrogen peroxide is present, the following oxidation reaction proceeds rapidly and the hue stabilization can be achieved.

． _{Cu + H 2 O 2 + 4NH} 3 → [Cu (NH 3) 4] 2+ + 2OH -

It is presumed that in the reaction, an oxide of Zn (standard generation free energy ΔGCuO (-14)> Cu ₂ O (-35)> ZnO (-76)) having an affinity for oxygen better than Cu is formed at the most. surface layer. Therefore, when the copper-zinc alloy forms the surface of the base material, if the gas phase oxidation is performed, the zinc ratio (Zn / Cu) in the outermost layer tends to be higher than the composition of the copper-zinc alloy as a base material. It is not intended to limit the present invention by theory, but it is believed that according to this reaction mechanism, Zn is concentrated in the oxide layer, thereby forming a dense oxide layer.

When performing the reaction, a group selected from the group consisting of ammonia concentration, oxygen concentration, other reactive gas concentrations, humidity in the reaction system, temperature in the reaction system, processing time, and temperature of the object can be selected. One or more groups are changed to control the hue. By changing only these parameters, the same equipment can be used, but multicoloring can be easily achieved.

In the case where the surface of the Cu-Zn alloy-tone processing, for example, a conventional chemical conversion treatment colored using base is used, the dissolution of Zn de-Zn reaction _{^{(Zn + 2OH - + 2H 2}} O → [Zn (OH) 4] ^2- + H ₂ ) proceeds simultaneously with the oxidation reaction of Cu and Zn, and the oxide film becomes a porous structure due to the de-Zn reaction (ionization tendency: Cu <Zn). Therefore, the color deviation may increase, and the friction resistance is firm. Performance may be degraded. However, according to gas-phase oxidation, zinc is only oxidized in the gas-phase reaction (Zn + 1 / 2O ₂ → ZnO) and does not dezincify. Therefore, no huge pores are observed. Compared with the chemical conversion treatment, a dense film can be obtained. Structure, which can improve the fastness to rubbing.

In order to achieve further polychromaticity, not only oxides and / or hydroxides, but also one or more compounds such as carbonates, sulfides, and sulfates of metals can be generated on the surface of fastener members. In the case of copper, the carbonate is yellow. green. Blue, sulfide is black, and sulfate is blue. By changing the composition ratio of these metal compounds and the depth of the surface reaction, more hue can be changed. As a method for generating various metal compounds on the surface of a fastener member, the methods described above are listed. A method of adding a reaction material that generates a desired metal compound during processing or gas phase oxidation.

For example, in order to carry out gas-phase oxidation, a gas used in water or an aqueous solution in which a desired compound capable of coloring to a target color is dissolved is used as a gas to be supplied, whereby the gas carries moisture, and therefore Can change the hue. For gas-phase oxidation, a halogen gas (Cl ₂ , Br _2, etc.), carbon dioxide (CO ₂ ), hydrogen peroxide, or the like may be added. In the metal activation treatment, the hue can also be adjusted by using an aqueous solution of a desired compound that can be colored to a target color. Examples of the aqueous solution include aqueous solutions of inorganic acids such as hydrochloric acid, sulfuric acid, peroxodisulfuric acid, nitric acid, chromic acid, and phosphoric acid, or acetic acid and dibasic acids (oxalic acid, malonic acid, succinic acid, and aspartic acid). Etc.) An aqueous solution of an organic acid, an aqueous solution of a salt such as carbonate, sulfate, peroxodisulfate, sulfide, or hydrogen peroxide.

From the viewpoint of removing residual components, it is preferable to wash unreacted components (for example, ammonia) adhering to the surface of the substrate after vapor-phase oxidation. In addition, after gas-phase oxidation, if necessary, one or two or more kinds of surface treatments such as rust prevention treatment, transparent lacquer coating, and waxing may be performed. Although not limited, the surface treatment can be performed by immersing in each surface treatment liquid, spraying the surface treatment liquid, dropping, coating, roll coating, and flow coating.

As described above, according to the present invention, there is provided a method for processing a color tone of an object, comprising: forming an oxide layer by subjecting an object having a substrate including a copper alloy containing zinc at least on its surface to gas phase oxidation in the presence of oxygen, The oxide layer is adjacent to the surface of the substrate, and the ratio A of the average zinc concentration to the average copper concentration in the oxide layer is A Higher than the ratio B of the average zinc concentration to the average copper concentration in the surface of the substrate. Furthermore, according to the present invention, there is provided a method for manufacturing a fastener, which includes using the color tone processing method. A fastener member to which the hue treatment of the present invention is applied can be used to produce a zipper or a daughter-in-law by a conventional method. For example, when the fastener member is a fastener element for a slide fastener, the hue treatment of the present invention is performed in a state of being assembled to a fastener chain, and then a slider, a pull tab, an upper stopper, Parts such as the lower stop and the opening and closing inserts complete the zipper.

(2-3 gas phase oxidation device)

Next, a configuration example of a gas-phase oxidation device is described, which is a preferable gas-phase oxidation device in which at least a part of a long member having a portion containing at least a surface of a metal is used as a processing target and the processing target is continuously subjected to color tone processing. .

Examples of the elongated member including at least a part of the metal include fastener elements (zip fastener chains) in which fastener elements made of metal are sprocket and are provided with fastener element straps with fastener element rows attached to one side edge of the long fastener tape, A ball chain formed by connecting metal balls, or a linear metal fastener member or a metal wire member. Furthermore, a zipper assembly in which a slider, an upper stopper, a lower stopper and the like are attached to a zipper chain can also be cited. With this device, it is possible to implement a color tone processing method of at least a part of a long member having a portion including at least a surface of a metal, the color tone processing method including continuously introducing a metal fastener member in a longitudinal direction while introducing it to a maintenance In a reaction chamber having an atmospheric pressure or a negative pressure, the gas phase oxidation of the surface of the member is performed in the reaction chamber, and thereafter, the member is discharged from the outlet of the reaction chamber.

<2-3-1 First Embodiment>

A configuration example of a gas phase oxidation device that can be used in the hue treatment of the present invention will be described. Furthermore, in the description of a specific example related to the device, as a processing object, a zipper chain is taken as an example. The zipper chain is a pair of zipper fastener elements in which a fastener element row is mounted on one side edge of a long zipper strap. The fastener chain belt is obtained by engaging the sprocket rows facing each other.

FIG. 5 is a schematic front view of the vapor-phase oxidation device 110 according to the first embodiment. The gas phase oxidation device 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 transfer mechanism 122, The gas suction device 113 and the ammonia gas decomposition device 112, and the control device 118 can be used to control the operation of these machines. Corrosion resistance is ensured by using stainless steel, especially Vostian iron-based stainless steel, in contact with the gas for gas phase oxidation.

The zipper chain 120 continuously passes the gas-phase reaction chamber 115 located inside the gas-phase oxidation device 110 in the direction of the arrow by the transfer mechanism 122. The transport mechanism 122 includes a plurality of guide rollers 122 a, and the zipper chain 120 passes through the gas-phase reaction chamber 115 while being guided by the plurality of guide rollers 122 a. One or more of the plurality of guide rollers 122 a are connected to a drive source such as a motor, and may be a drive source of the fastener chain 120 itself. In addition, a drive source 122b is provided outside the downstream side of the gas-phase oxidation device 110, and the zipper chain 120 may be transported by an external traction method.

The gas supply system 114 for gas phase oxidation in the first embodiment includes a gas storage unit 114a, a gas pipe 114b, and a gas outlet 114c. The vapor-phase oxidation gas stored in the gas storage unit 114a is self-gassed through the gas pipe 114b. The body ejection outlet 114c is supplied into the gas-phase reaction chamber 115. In the case where there are many kinds of gas used in the opposite direction, a plurality of gas storage units may also be provided. In the first embodiment, in addition to the gas storage unit 114a, a gas storage unit 114d is also provided. The gas for oxidation in the gas phase from the gas storage unit 114d passes through the gas pipe 114b and is used for gas phase oxidation from the gas storage unit 114a. The gases are pre-mixed. As an example, ammonia may be stored in the gas storage unit 114a, and air may be stored in the gas storage unit 114d. Air can also use compressed air from a compressor instead of a gas storage unit.

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

The fastener chain 120 passes through the gas-phase reaction chamber 115 in the presence of a gas-phase oxidation gas, and undergoes a hue treatment based on the oxidation reaction. The gas in the gas-phase reaction chamber 115 is sucked by a gas suction device 113 such as a blower, and sucked by a suction port 121 provided near the outlet, and is discharged to the outside of the gas-phase reaction chamber 115 through a pipe 123. Unreacted ammonia is decomposed into H ₂ O and N _{2 and} then discharged to the outside of the gas-phase oxidation device 110. The ammonia decomposition method is not particularly limited, and examples thereof include a catalyst decomposition type, a combustion type, a gas decomposition type, and a wet scrubber type. In addition, the ammonia gas decomposition device is preferably installed as necessary, but it is not necessarily required 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 greater than the gas discharge amount from the discharge port 114c, the inside of the gas-phase reaction chamber 115 can be maintained at a negative pressure. Thereby, the gas in the gas-phase reaction chamber 115 can be prevented from leaking to the outside. However, in order to further stably perform the gas phase treatment in an environment having a fixed concentration, it is preferable to provide water at the inlet 115in side (upstream side) and / or the outlet 115out side (downstream side) of the gas phase reaction chamber 115 Sealing unit 116. In consideration of the air-tightness in the gas-phase treatment tank, the water-sealing unit 116 may be provided only on one of the inlet 115in side and the outlet 115out side, preferably at least on the outlet side, and more preferably on the outlet side. On both sides. Among them, if the water-sealing unit 116 is provided on the side of the inlet 115in, the zipper chain 120 is wetted. Therefore, color unevenness is likely to occur during the color tone treatment of the vapor phase oxidation. Therefore, from the viewpoint of preventing color unevenness, it is preferable not to provide the water seal unit 116 on the inlet 115in side. In this case, if the inside of the gas-phase reaction chamber 115 is maintained at a negative pressure, air enters the gas-phase reaction chamber 115. Therefore, the air may be supplied without passing through the gas pipe 114b, or may be supplied in combination with the air from the gas pipe 114b.

On the other hand, in emergency situations, water seals can be used to facilitate safety management. Therefore, in the first embodiment, the water seal unit 116 is provided on both the inlet 115in side and the outlet 115out side. However, during normal operation, water seal is performed only on the outlet 115out side, and not on the inlet 115in side.

The gas-phase oxidation device 110 preferably includes a gas flow control mechanism. The control mechanism 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. This is particularly effective from the standpoint of preventing gas leakage when the water seal unit 116 on the outlet 115out side is used for water sealing, while the water seal unit 116 is not provided on the inlet 115in side or is not used for water seal even if installed. It includes such a flow control mechanism. On the other hand, it corresponds to the third embodiment described later. In the case where the water seal unit 116 on the inlet 115in side is used for water sealing, and the water seal unit 116 is not provided on the outlet 115out side or even if it is not used, it is more Preferably, it is controlled so that the gas phase oxidation gas supplied into the gas phase reaction chamber 115 flows from the outlet 115out side to the inlet 115in side.

The airflow control mechanism is not particularly limited. In the first embodiment, the airflow control mechanism includes at least one ejection port 114c provided in the gas-phase reaction chamber 115 for supplying a gas-phase oxidation gas, and the gas-phase oxidation gas. The gas in the reaction chamber 115 is discharged to at least one suction port 121 outside the gas-phase reaction chamber 115. Further, the suction port closest to the outlet side among the at least one suction port 121 is arranged closer to the outlet 115out side than any of the at least one discharge port 114c, and is supplied to the gas phase in the gas-phase reaction chamber 115. The oxidation 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 closer to the outlet 115out than any one of the at least one discharge port 114c. Furthermore, by setting the total gas suction amount from the at least one suction port 121 to be larger than the total gas discharge amount from the at least one discharge port 114c, the inside of the gas-phase reaction chamber 115 becomes a negative pressure, thereby preventing gas leakage.

The zipper chain 120 is discharged from the gas-phase reaction chamber 115 through the water sealing unit 116 (outlet), and the gas in the gas-phase reaction chamber 115 can be shut off from the outside, and the zipper chain 120 can be discharged at the same time. In addition, an NH ₃ sensor (not shown) may be provided on the outside air side of the gas-phase oxidation device 110. When NH ₃ flows out, the NH ₃ sensor (not shown) senses it and can stop the supply of NH ₃ by a command from the control device 118.

In addition, the control device 118 can control the flow rate of the gas phase oxidation gas supplied into the gas phase reaction chamber 115 from the gas phase oxidation gas storage units 114a and 114d through the ejection outlet 114c, and can control the gas phase reaction chamber. The gas concentration in the chamber 115 is controlled. The gas-phase oxidation device 110 can be installed in a constant-temperature humidity control box, whereby air with controlled temperature and humidity can be introduced into the gas-phase oxidation device 110. The temperature in the gas-phase reaction chamber 115 can be controlled by a heating unit (not shown).

While the zipper chain 120 is being transported by the transport mechanism 122, it passes through the water-sealing unit (upstream) 116 (not water-sealed during normal operation, but water-sealed only during extraordinary hours) and enters the gas-phase reaction chamber 115. Thereafter, the gas for gas phase oxidation supplied into the gas phase reaction chamber 115 reacts with a copper alloy constituting the surface of the fastener elements of the fastener chain 120 which has been subjected to the pretreatment, and changes the color tone by the reaction mechanism. After that, the zipper chain 120 is discharged from the gas-phase oxidation device 110 through the water-sealing unit (downstream) 116 while being transferred by the transfer mechanism 122. The unreacted gas adhering to the zipper chain 120 is immersed in water when passing through the water sealing unit (downstream) 116, and is therefore cleaned and removed.

<2-3-2 Second Embodiment>

FIG. 6 schematically illustrates a front surface of a vapor phase oxidation device 210 according to a second embodiment. Illustration. Unless otherwise specified, the reference signs in FIG. 6 have the same meanings as the reference signs explained in the first embodiment, and therefore description thereof is omitted. When the installation area is reduced, the vapor-phase oxidation device 210 of the second embodiment is an effective embodiment. In the case where the installation space in the planar direction is small, it can be called a particularly advantageous embodiment. In the second embodiment, a control device also exists, but the illustration is omitted.

In the second embodiment, the gas-phase reaction chamber 115 includes a first chamber 115a on the entrance side, a second chamber 115b on the exit side, and a third chamber 115c on the first chamber 115a and the first chamber 115a. Between two chambers 115b. The transport mechanism 122 is configured to allow the object to pass through the first chamber 115a, the third chamber 115c, and the second chamber 115b in this order, and may include a guide roller 122a to include a vertical upward direction and a vertical downward direction. Either or both are directions in which the zipper chain 120 passes through the third chamber 115c. The fastener chain 120 is carried by a drive source 122 b provided outside the downstream side of the vapor-phase oxidation device 210.

When the conveying distance of the zipper chain 120 when passing through the gas-phase reaction chamber 115 is set to the same condition, the vertical upward direction and / or the vertical downward direction exist as the direction for conveying the zipper chain 120, thereby horizontally The conveying distance is shortened, so that the installation area of the vapor-phase oxidation device 210 can be reduced.

In the second embodiment, the third chamber 115c includes: an upper portion of the third chamber 115c1, which is located at the same height as the first chamber 115a and the second chamber 115b; and a lower portion 115c2, which is located higher than the third chamber The upper part of the chamber is further lower, and the transfer mechanism 122 is configured to allow the zipper chain 120 to pass through the first chamber 115a, the third chamber upper part 115c1, the third chamber lower part 115c2, and the second chamber 115b.

In the second embodiment, the zipper chain 120 passes through the first chamber in the horizontal direction, and then enters the third chamber 115c. The zipper chain 120 moves back and forth between the third chamber upper part 115c1 and the third chamber lower part 115c2 while moving in the vertical direction in the third chamber 115c (in the second embodiment, the number of round trips is two Times), then enter the second chamber 115b, and thereafter, it is discharged from the gas-phase oxidation device 210 by the water-sealing unit 116 on the outlet side.

As the ratio of the vertical transport distance in the third chamber 115c is increased, the installation area of the gas phase oxidation device 210 can be reduced. From the viewpoint of saving installation space, it is preferable that the total transport distance d1 of the zipper chain 120 in the third chamber 115c in the vertical direction is longer than the horizontal direction in the first chamber 115a and the second chamber 115b. The total transport distance d2 in the direction is more preferably d1 / d2 ≧ 2, more preferably d1 / d2 ≧ 3, and even more preferably d1 / d2 ≧ 4. The upper limit of d1 / d2 does not exist, but it is usually d1 / d2 ≦ 20, and typically d1 / d2 ≦ 10.

The guide roller 122 provided in the lower part 115c2 of the third chamber may be a dancer roller. By moving the tension adjusting roller up and down, it can be effectively used as a unit for adjusting the tension on the zipper chain 120 to be conveyed. In addition, by changing the installation position of the tension adjustment roller in the vertical direction according to the type of the zipper chain 120, the distance that the zipper chain 120 passes in the gas-phase reaction chamber 115 can also be adjusted. Thereby, it is also possible to obtain the advantage that the processing time can be changed without changing the conveying speed of the zipper chain 120, and it is easy to impart changes to the shades of color.

It is preferable that at least one ejection port 114c of the gas phase oxidation gas is provided in the lower part 115c2 of the third chamber, and more preferably, it is lower than the zipper chain 120 in the lower part of the third chamber At least one ejection port 114c of the gas-phase oxidation gas is provided at the position of the lowest point through which 115c2 passes. This makes it possible to improve the uniformity of the concentration of the gas phase oxidation gas in the lower portion 115c2 of the third chamber.

Since the vapor-phase oxidation gas flows into the third chamber 115c, the concentration of the vapor-phase oxidation gas in the third chamber 115c tends to be higher than that of the first chamber 115a and the second chamber 115b. By disposing the third chamber 115c between the first chamber 115a and the second chamber 115b, there is less danger of gas phase oxidation gas leaking to the outside of the apparatus, and the safety of the gas phase oxidation apparatus 210 is improved.

In addition, in the second embodiment, the water seal unit 116 is provided only on the outlet side. Therefore, from the viewpoint of preventing gas leakage, the gas-phase oxidation device 210 is preferably provided with at least one of the suction ports 121 in the second chamber 115b on the outlet side, and more preferably has suction in the second chamber 115b only. Mouth 121. In the second embodiment, the vapor-phase oxidation gas flowing into the lower part 115c2 of the third chamber moves to the upper part 115c1 of the third chamber, and at least a part of the gas is used for the oxidation reaction of the zipper chain, and passes through the second chamber 115b to self-suction the mouth. 121 is discharged.

In the case of the first embodiment, for example, when ammonia is used as the gas and the gas is applied in the opposite direction, ammonia is lighter than air, so it is easy to move upward, and there is a possibility that a concentration distribution is generated in the gas phase reaction chamber 115. Therefore, it is possible to impair the uniformity of hue in the up-down direction of the fastener chain 120. In contrast, in the case of the second embodiment, since the zipper chain 120 in the lower part 115c2 of the third chamber is transported in the vertical direction (vertical direction), the concentration of the gas-phase reaction gas is generated even in the vertical direction. Of the distribution on the uniformity of the hue in the vertical direction of the zipper chain 120 Also suppressed. Therefore, the second embodiment is also advantageous in that the uniformity of hue on the front and back of the fastener chain 120 can be improved.

<2-3-3 Third Embodiment>

FIG. 7 is a front view schematically showing a vapor-phase oxidation device 310 according to a third embodiment. Unless otherwise specified, the reference signs in FIG. 7 have the same meanings as the reference signs explained in the first embodiment, and therefore description thereof is omitted. The third embodiment differs from the first embodiment in that in the third embodiment, the water-sealing unit 116 on the outlet side is not used for water-sealing, and the water-sealing unit 116 on the inlet side is used only during normal operation. In water seal. According to this embodiment, since the zipper chain 120 is wet immediately before being subjected to vapor-phase oxidation, color unevenness is liable to occur in the zipper chain 120 after the color tone treatment. However, when the color unevenness is allowed or it is desired that the color unevenness occurs In the case of the generated pattern, it can be called a preferred embodiment.

In addition, in the third embodiment, the installation position of the water seal unit 116 is changed to the inlet 115 in side of the gas-phase reaction chamber 115. Therefore, the gas-phase oxidation device 310 preferably includes a gas flow control mechanism. Control is performed so that the gas for oxidation in the gas phase supplied to the gas phase reaction chamber 115 flows from the outlet side to the inlet side. In the case where the water-sealing unit 116 on the inlet side is used for water sealing and the water-sealing unit 116 on the outlet side is not provided or even if it is not used, it is effective from the viewpoint of preventing gas leakage. Includes this type of airflow control mechanism. The airflow control mechanism is not particularly limited. In the third embodiment, the airflow control mechanism includes at least one ejection port 114c provided in the gas-phase reaction chamber 115 for supplying a gas-phase oxidation gas, and the gas-phase oxidation chamber 114c. Gas exhaust in reaction chamber 115 At least one suction port 121 exiting the gas-phase reaction chamber 115. In addition, the suction port closest to the inlet 115in side of the at least one suction port 121 is disposed closer to the inlet 115in side than any of the at least one discharge port 114c, and the gas supplied to the gas-phase reaction chamber 115 is The phase oxidation 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 side than any of the at least one discharge port 114c. Furthermore, by setting the total gas suction amount from the at least one suction port 121 to be larger than the total gas discharge amount from the at least one discharge port 114c, the inside of the gas-phase reaction chamber 115 becomes a negative pressure, thereby preventing gas leakage.

With this configuration, the gas in the gas-phase reaction chamber 115 is sucked from a suction port 121 provided near the inlet 115in of the gas-phase reaction chamber 115 by a gas suction device 113 such as a blower, and is discharged to the gas-phase reaction chamber. Room 115 outside.

(2-4 tone processing system)

FIG. 8 shows a configuration example of the hue processing system 30 for continuously performing the pre-processing, vapor-phase oxidation, and rust-prevention processing described so far. The color tone processing system 30 is sequentially provided with a degreasing device 31, a water washing device 32, a gas phase oxidation device 34, a water washing device 35, a rust prevention processing device 36, a drying device 37, a surface processing device 38, and a drying device 39. A long zipper component 41 such as a zipper chain is transported in a roll-to-roll direction, and while passing through these devices in order, it can be subjected to a predetermined process to perform a color tone process. The surface treatment device 38 can perform surface treatment such as clear lacquer coating and waxing.

[Example]

Examples of the present invention are shown 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)

Prepare a metal zipper chain with a length of 200mm ~ 250mm after degreasing and washing. The elements of the metal zipper chain are made of copper-zinc alloy (Cu: 85% by mass (85.4at.%), Zn: 15% by mass (14.6at.%)). The composition is a value without considering unavoidable impurities, and the composition of the fastener element may include unavoidable impurities. The same applies to the following test examples. The sprocket row is formed by pressing a Y-shaped rod that has been annealed in a reducing environment into a sprocket shape, and is pressurized and fixed to a fastener tape.

The zipper chain was placed in a batch processing device of a gas-phase reaction tubular furnace (Φ75mm quartz tube (0.6L capacity)), and under the reaction conditions shown in Table 1, gas-phase oxidation was performed using a mixed gas of air and ammonia gas. . After the gas-phase oxidation, it was washed with water in 2 L of water, immersed in an aqueous solution of benzotriazole for 1 minute to perform rust prevention treatment, and then washed with water and naturally dried. In addition, neither the clear lacquer coating nor waxing was performed.

(Test Example 2)

Prepare a metal zipper chain with a length of 200mm ~ 250mm after degreasing and washing. The fastener element rows of the metal zipper chain are made of copper-zinc alloy (Cu: 65 mass% (65.7at.%), Zn: 35 mass% (34.3at.%)). The sprocket row is formed by pressing a Y-shaped rod that has been annealed in an oxidizing environment into a sprocket shape, and press-fixed to the fastener tape. Place this zipper chain in a gas-phase reaction tubular furnace batch processing device (Φ75mm In a quartz tube (0.6 L volume)), under the reaction conditions shown in Table 1, a gas mixture of air and ammonia was used for gas phase oxidation. The same anti-rust treatment as in Test Example 1 was performed on the zipper chain after gas-phase oxidation. In addition, neither the clear lacquer coating nor waxing was performed.

(Test Example 3)

Prepare a metal zipper chain with a length of 200mm ~ 250mm after degreasing and washing. The fastener elements of the metal zipper chain are made of copper-zinc alloy (Cu: 60% by mass (60.7at.%), Zn: 40% by mass (39.3at.%)). The sprocket row is formed by pressing a Y-shaped rod that has been annealed in an oxidizing environment into a sprocket shape, and press-fixed to the fastener tape. The zipper chain was placed in a batch processing device of a gas-phase reaction tubular furnace (Φ75mm quartz tube (0.6L capacity)), and under the reaction conditions shown in Table 1, gas-phase oxidation was performed using a mixed gas of air and ammonia gas. . The same anti-rust treatment as in Test Example 1 was performed on the zipper chain after gas-phase oxidation. In addition, neither the clear lacquer coating nor waxing was performed.

(Test Example 4)

The same fastener chain as in Test Example 1 was colored using a chemical conversion treatment in a liquid phase instead of a gas phase oxidation. Specifically, chemical conversion treatment is performed by immersing the zipper chain washed with degreasing water in a chemical conversion treatment liquid. After the chemical conversion treatment, the same rust prevention treatment as in Test Example 1 was performed. In addition, neither the clear lacquer coating nor waxing was performed.

(Test Example 5)

For the same fastener chain as in Test Example 2, a liquid phase chemical conversion treatment was used instead Gas-phase oxidation is used for coloring. Specifically, chemical conversion treatment is performed by immersing the zipper chain washed with degreasing water in a chemical conversion treatment liquid. After the chemical conversion treatment, the same rust prevention treatment as in Test Example 1 was performed. In addition, neither the clear lacquer coating nor waxing was performed.

(Test Example 6)

The same fastener chain as in Test Example 3 was colored using a chemical conversion treatment in a liquid phase instead of a gas phase oxidation. Specifically, chemical conversion treatment is performed by immersing the zipper chain washed with degreasing water in a chemical conversion treatment liquid. After the chemical conversion treatment, the same rust prevention treatment as in Test Example 1 was performed. In addition, neither the clear lacquer coating nor waxing was performed.

Regarding Test Example 1 to Test Example 6, the obtained hue changed depending on the processing time and the concentration of the processing gas or liquid, but changed to yellow → reddish brown → brown → black with brown depending on the time and concentration. In addition, the estimated composition of the oxide film at this time is oxidized copper such as Cu ₂ O or CuO.

<Various performance tests>

Each sample of the metal zipper chain of Test Examples 1 to 6 was evaluated for performance of mechanical characteristics, and the obtained results are shown in Table 1.

The "English resistance L-class" refers to a test using the method of Japanese Industrial Standards (JIS) S 3015: 2007 (endurance test for round trip switches). In all samples, an evaluation of "500 times without abnormality" was obtained. "500 times without abnormality" means the following case: as long as the slider is attached to the zipper chain with a slider, a jig, etc., the slider can also be used as a back and forth movement 500 times relative to the zipper chain. The function of the zipper is normal.

The "friction fastness" is a test for dyeing a sprocket, that is, a test using the methods of JIS L 0803: 2011 and JIS L 0849: 2013. The fastness to rubbing was evaluated by visually observing the presence or absence of dirt (caused by adhesion and peeling) when the surface of the sprocket surface in contact with the test cloth after the test.

Without dirt: ○

With dirt: ×

<Depth direction analysis of oxide layer>

For each sample of the metal zipper chain of Test Example 1 to Test Example 6, the sprocket after the gas phase oxidation or chemical conversion treatment and before the rust prevention treatment was performed using an Auje electronic spectroscopic device equipped with a Field Emission electron gun. AES analysis was performed on the surface to obtain a deep profile. The conditions for AES analysis were an acceleration voltage of the electron gun of 10 kV, a current amount of 3 × 10 ^-8 A, a beam diameter of 50 μm, and a sample tilt of 30 °. An Ar monomer ion gun 2 kV was used for etching. The detection depth is calculated using an etching rate of SiO ₂ standard material of 8.0 nm / min, and is converted based on the sputtering time. The etching rate is a value obtained by dividing 100 times the intensity of O of a SiO ₂ standard material (a thermally oxidized film of 100 nm on a Si substrate) by half.

The atomic concentrations of Cu, Zn, and O are calculated by setting the relative sensitivity coefficients to Cu: 1, Zn: 1, and O: 1. The average Zn concentration, the average Cu concentration, and the average O concentration in the oxide layer are the average values of the measured values using a depth of 10 nm to 20 nm on the surface of the self-oxidized layer. The boundary between the oxide layer and the substrate (substrate surface) with an O concentration of 5 at.% To 20 nm The average of the measured values up to the depth. For reference, the depth sections of Test Example 3 and Test Example 6 are shown in FIGS. 3 and 4.

[Table 1-2]

According to the results in Table 1, the results of the British resistance L-level test of each sample of Test Example 1 to Test Example 3 are the same as the conventional chemical treatment (Test Example 4 to Test Example 6), but regarding the fastness to friction, the test examples The samples from 1 to Test Example 3 were better than Test Examples 4 to 6.

<Depth Analysis of the Oxidation Layer of the Sample with the Finished Layer>

For each sample of the metal zipper chain of Test Example 1 to Test Example 3, after the gas phase oxidation, anti-rust treatment and transparent lacquer coating were sequentially performed. The object was immersed in a release agent (S-BACK H-300: Sasaki Chemical Co., Ltd.) at room temperature for one night, and the transparent lacquer coating and the anti-rust treatment layer were removed from each dried sample to expose the surface of the chain teeth. Oxide layer. Then, the depth direction analysis of the oxide layer was performed by the method described above. As a result, in any sample, substantially the same test result as that before the formation of the finished layer was obtained.

Claims (26)

An object having a metal surface includes: a substrate (11), at least the surface of which contains a copper alloy containing zinc; and an oxide layer (12), which is adjacent to the surface of the substrate (11), and the oxide layer ( 12) The surface as a reference, 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 is higher than the average zinc concentration relative to the average copper concentration in the surface of the substrate (11) Than B. The object according to item 1 of the scope of patent application, wherein the average zinc concentration on the surface of the substrate (11) is 5 at.% To 50 at.%. The object according to claim 1 or claim 2, wherein the ratio A / B of the ratio A to the ratio B is 2.0 or more. The object according to claim 1 or claim 2, wherein the base material (11) as a whole contains a copper alloy containing zinc. The object according to item 4 of the scope of patent application, wherein, based on the surface of the oxide layer (12), the average zinc concentration in the range from a depth of 10 nm to a depth of 20 nm is 5 at.% To 80 at.% . The object according to item 1 or 2 of the scope of patent application, wherein the object is a zipper member. A zipper includes an object as described in item 6 of the scope of patent application. An object tone processing method comprising subjecting an object having a substrate including a copper alloy containing zinc at least on its surface to gas phase oxidation in the presence of at least oxygen, thereby forming an oxide layer by gas phase oxidation, said The oxide layer is adjacent to the surface of the substrate, and based on the surface of the oxide layer, the ratio A of the average zinc concentration to the average copper concentration in a range from a depth of 10 nm to a depth of 20 nm is higher than that in the surface of the substrate. The ratio B of the average zinc concentration to the average copper concentration. The hue processing method for an object according to item 8 of the scope of patent application, wherein gas phase oxidation is performed in the presence of ammonia. The color tone processing method for an object according to item 8 or item 9 of the scope of patent application, wherein the method is selected from the group consisting of the concentration of ammonia, the concentration of oxygen, the concentration of other reactive gases, the humidity in the reaction system, and the reaction system. One or more of the group consisting of the internal temperature, the processing time, and the temperature of the object are changed to perform the hue control of the gas-phase oxidation. The color tone processing method for an object according to item 8 or item 9 of the scope of patent application, wherein the object is a fastener member. The color tone processing method for an object according to item 8 or item 9 of the scope of the patent application, wherein the gas phase oxidation is performed at an ambient temperature of 20 ° C to 80 ° C. The hue processing method for an object according to item 8 or item 9 of the scope of patent application, wherein the gas phase oxidation is performed under negative pressure. The color tone processing method for an object according to item 8 or item 9 of the scope of patent application, which comprises sequentially performing activation treatment and water washing on the surface of the substrate before performing the gas phase oxidation. The color tone processing method for an object according to item 8 or item 9 of the scope of patent application, which comprises sequentially degreasing and washing the surface of the substrate before performing the gas phase oxidation. The color tone processing method for an object according to item 8 or item 9 of the scope of patent application, which comprises performing, on the surface of the oxide layer formed by the gas phase oxidation, selected from the group consisting of a transparent coating, an antirust treatment, and a wax coating. At least one or more surface treatments in the group. A gas-phase oxidation device for implementing a color tone processing method includes: a gas-phase reaction chamber (115) having an inlet (115in) and an outlet (115out) for gas-phase oxidation; and a transport mechanism (122) for So that at least a part of the elongated member having a portion containing at least a surface of the metal enters from the inlet (115in), passes through the gas-phase reaction chamber (115), and is continuously sent out from the outlet (115out); A nozzle (114c) is used to supply a gas phase oxidation gas into the gas phase reaction chamber (115); and a suction port (121) is used to supply the gas in the gas phase reaction chamber (115). The gas is discharged outside the gas-phase reaction chamber (115). The gas-phase oxidation device according to item 17 of the scope of patent application, wherein either or both of the outlet (115out) side and the inlet (115in) side of the gas-phase reaction chamber (115) A water sealing unit (116) is provided to block the gas inside the gas-phase reaction chamber (115). The gas-phase oxidation device according to claim 18, wherein the gas-phase reaction chamber (115) is provided only on the outlet (115out) side of the gas-phase reaction chamber (115). ) The water sealed unit (116) is interrupted by the internal gas and the external. The gas-phase oxidation device according to item 19 of the scope of application for a patent, which includes a gas flow control mechanism that allows the gas for gas-phase oxidation supplied to the gas-phase reaction chamber (115) to be self-contained. The manner in which the inlet (115in) side flows to the outlet (115out) side is controlled. The gas-phase oxidation device according to claim 20, wherein the gas flow control mechanism includes at least one ejection port provided in the gas-phase reaction chamber (115) for supplying gas for gas-phase oxidation. (114c) and at least one suction port (121) for exhausting the gas in the gas-phase reaction chamber (115) to the outside of the gas-phase reaction chamber (115), and the at least one suction port ( All the suction openings in 121) are arranged closer to the exit (115out) than all the discharge openings (114c) in the at least one discharge opening (114c). The gas-phase oxidation device according to item 21 of the scope of patent application, wherein the transfer mechanism (122) is configured to include one or both of a substantially vertical upward direction and a substantially vertical downward direction as the object in the gas phase. The direction of passage in the reaction chamber (115). The gas-phase oxidation device according to item 22 of the scope of patent application, wherein the gas-phase reaction chamber (115) includes a first chamber (115a) located on the side of the inlet (115in); a second chamber (115b) is located on the exit (115out) side; and a third chamber (115c) is located between the first chamber (115a) and the second chamber (115b), and the transfer mechanism ( 122) is configured to allow the object to pass through the first chamber (115a), the third chamber (115c), and the second chamber (115b) in sequence, and is configured to include a substantially vertical One or both of the upward direction and the substantially vertical downward direction are directions in which the object passes through the third chamber (115c). The gas-phase oxidation device according to item 23 of the scope of patent application, wherein the third chamber (115c) includes: an upper portion of the third chamber (115c1), which is located between the first chamber (115a) and the first chamber (115a). The second chamber (115b) has the same height; and the lower chamber (115c2) of the third chamber is located at a lower side than the upper portion (115c1) of the third chamber, and the transfer mechanism (122) is configured so that The object passes through the first chamber (115a), the third chamber upper portion (115c1), the third chamber lower portion (115c2), and the second chamber (115b). The gas-phase oxidation device according to item 23 or 24 of the patent application scope, wherein at least one of the ejection ports (114c) is provided in the lower portion (115c2) of the third chamber, and the second chamber is provided in the second chamber. (115b) At least one of the suction ports (121) is provided. The gas-phase oxidation device according to item 23 or 24 of the scope of application for a patent, wherein the transfer mechanism (122) is configured to include both a substantially vertical upward direction and a substantially vertical downward direction as the object. The direction of passage in the third chamber (115c) will be described.