JP2019189937A - Method and apparatus for forming functional layer on surface of metal base material layer - Google Patents

Abstract

To provide a method for forming a functional layer on the surface of a base material layer, capable of forming a functional layer, such as a resin coating layer and a plating layer on the surface of the base material layer by simple work, forming a new functional layer with high adhesion and reducing work time and work load.SOLUTION: The method for forming a functional layer on the surface of a base material layer comprises the steps of: contacting superheated steam to the surface of the base material layer to remove contamination (including an oxide film), etc., adhering to the surface and simultaneously, temporarily extend a surface depression, a crack and a space between molecules or atoms; contacting a catalyst layer formation agent including catalyst layer formation molecules to the surface to penetrate the catalyst layer formation molecules into the space and bonding them with the surface of the base material layer to form a catalyst layer; and forming a functional layer in at least a part of the surface of the catalyst layer. The surface of the base material layer is activated by contacting the superheated steam on the surface, and the activated surface and the catalyst layer formation molecules are bonded.SELECTED DRAWING: Figure 1

Description

  When the present invention forms a functional layer on the surface layer of a base layer of a metal or metal alloy for the purpose of various functions such as rust prevention, corrosion prevention, protection, water permeation suppression, decoration, weight reduction of the base layer, The present invention relates to a method capable of integrally forming a functional layer on the surface layer with high adhesion and an apparatus therefor.

Typical examples of the functional layer for the purpose described above formed on the surface layer of the base material layer include plating and resin coating. Among these, the plating includes a wet method in which the treatment is performed in a solution in which a metal is dissolved and a dry method in which the treatment is performed in a vacuum, and is a technique for forming a thin metal film on the surface layer of the base material layer.
Resin coating is a technique for forming a resin coating layer by bringing a resin paint into contact with a surface layer of a base material layer. Furthermore, a technique for reducing the weight by joining different materials of metal and resin with an adhesive has been used.
Conventionally, in order to improve the adhesion between the surface layer of the base material layer and the functional layer, first, the surface layer of the base material layer is first removed to remove dirt, roughen, or improve the familiarity with the functional layer. Etc. are done.

  Here, in order to firmly adhere the functional layer to the surface layer of the base material layer described above, an organic solvent, an alkaline cleaning agent, pickling (etching), or the like has been used. Furthermore, depending on the state of the surface, a clean and active surface layer was obtained by removing a functional layer or dirt (including an oxide film) on which the base material deteriorated by polishing with kelen or blast. Patent Document 1 discloses removal of impurities such as an oxide film generated on a metal surface layer, and the surface layer of the base material layer is also activated by using such pickling (etching). Yes.

JP 2011-20006 (see, for example, paragraph 0011) JP 2012-237064 A

  However, the active surface obtained by either method oxidizes in contact with oxygen in the atmosphere to form a stable oxide film, so that a functional layer is formed on this oxide film and has excellent adhesion strength. It was difficult to bond with. In order to solve such a problem, the applicant of the present application has modified the surface properties of an alloy containing iron or titanium as a main component, thereby improving the adhesion with a functional layer such as a resin. It has proposed in patent document 2 which is a quality agent and a processing method.

According to the method described in Patent Document 2, the operation of forming a coupling layer that delays the formation of an oxidation-stable film on the active surface by using a chemical polishing solution can be applied to a relatively small and small one. However, its use for large products and structures installed outdoors is remarkably restricted from the viewpoint of protecting the surrounding environment.
The present invention has been made in view of the above problems, and can be used for large products and structures installed outdoors, without adversely affecting the surrounding environment, and By forming a catalyst layer on the surface layer of the base material layer with a simple operation, the functional layer such as the conventional resin coating layer and plating layer can be reduced, and the functional layer can be applied with high adhesiveness in every detail. It is an object to provide a method of forming and an apparatus capable of automating the implementation of this method.

  As a result of intensive studies by the inventors of the present invention, depending on the composition of the base material, an acidic aqueous solution (PH 5.8 or less to about 0.1) such as halogen-based inorganic acid, fruit acid, and electrolytic acid water, or water, or An alkaline aqueous solution (PH8.6 or more to about 12.5) is selected in a timely manner, and the surface layer is first brought into contact with the substrate surface as superheated steam, and the surface layer is removed and at the same time numerous fine dents (A and B in FIG. 7). See) and cracks (see C), or dents and cracks in the surface layer, or the interstitial or interatomic gaps of the crystal structure forming the surface layer, thereby temporarily adhering or existing moisture. It was found that dirt and dirt can be removed. Based on such knowledge, the inventor of the present invention has come up with the method of the present invention in which a functional layer corresponding to various uses is firmly formed on the surface layer. The concept of the method of the present invention is shown in FIG. An embodiment included in the concept of the present invention is shown in FIG.

The invention described in claim 1 includes a step of bringing superheated steam into contact with the surface layer of the base material layer to temporarily widen the recesses, cracks, intermolecular or interatomic gaps in the surface layer, and catalyst layer forming molecules. The catalyst layer forming agent containing the catalyst layer is brought into contact with the surface layer, the catalyst layer forming molecules are allowed to enter the gap that has been temporarily expanded, the gap is then closed, and the catalyst is placed inside the gap. Forming a catalyst layer by confining layer-forming molecules and bonding the catalyst layer-forming molecules inside and outside the gap; and forming a functional layer on at least a part of the surface layer of the catalyst layer; (FIG. 6 (i)).
Moisture and the like evaporate from the above-mentioned part by contact with superheated steam, and the volume is reduced to become an active surface layer with latent heat of vacuum, and then an aqueous solution containing a component that forms a catalyst layer forming agent (simply The catalyst layer forming agent is absorbed by the surface layer of the base material layer by contacting (preferably contacting as superheated steam), and the latent heat and self-heating of the base material surface layer. It can be inferred that the moisture contained in the catalyst layer forming agent evaporates due to the involvement of the catalyst, and only a component is doped into the voids such as innumerable dents and cracks to form a catalyst layer firmly integrated with the substrate surface layer. .
In the present invention, “dirt” refers to segregated and coarsened crystal grains (including crystal grains and lumps having a high ionization tendency) generated during metal processing, gas bodies or / and inclusions that have entered the crystal grain boundaries. Furthermore, it refers to an oxide film covering the surface layer.

According to a second aspect of the present invention, the surface layer is activated by bringing superheated steam into contact with the surface layer of the base material layer, and the activated surface layer and the catalyst layer forming molecule are bound to each other. Also good.
By doing in this way, the catalyst layer couple | bonded with the base material layer more firmly can be obtained.

As the functional layer formed on the surface layer of the base material layer by the method of the present invention, as described in claim 3, an alloy layer, a compound layer, a mixture layer, a ceramic layer, a resin layer, a plating layer, or a protective layer It can be either.
As described in claim 4, a viscosity imparting agent may be added to the catalyst layer forming agent. Further, as described in claim 5, superheated steam may be contacted after the catalyst layer forming agent is contacted with the surface layer (FIG. 6 (vi)). This method is particularly effective when a catalyst layer is formed by coating or dipping.
The step of bringing the superheated steam into contact with the step of forming the catalyst layer can be simultaneously performed by adding a catalyst layer forming agent to the superheated steam aqueous solution. (Fig. 6 (ii) (v)).

According to a seventh aspect of the present invention, the catalyst layer forming agent may contain doping metal molecules, and examples of such doping metal molecules include metal ion molecules and metal oxide molecules.
Prior to the step of bringing superheated steam into contact with the surface layer of the base material layer, a step of bringing an acidic aqueous solution and an alkaline aqueous solution into contact with the base material layer according to the composition of the base material may be provided (FIG. 6 (iii) (iv)). The acidic aqueous solution and the alkaline aqueous solution may or may not be superheated steam.

As described in claim 8, the superheated steam may be an acidic aqueous solution, water or an alkaline aqueous solution, and as described in claim 9, after contacting the acidic aqueous solution with the surface layer, A neutral aqueous solution or this superheated steam may be brought into contact with the surface layer (see FIGS. 6 (iii) and (iv)).
For example, as shown in FIG. 5 (b), the contact process of the superheated steam to the surface layer of the base material layer, the contact of the catalyst layer forming agent, and the contact treatment method of the functional layer forming agent may be performed by a chamber or The region 5 is arranged in order from the upstream side to the downstream side, and each process is performed while moving the substrate W in the direction of arrow II by the conveyor 6 or the like from the upstream chamber or region 5 to the downstream chamber or region 5. A batch processing system that sequentially performs the above can be given.

Further, for example, as shown in claim 10 and FIG. 5A, a superheated steam generator for generating superheated steam and a plurality of spray nozzles arranged close to the base material layer are prepared, and the spray nozzle Are assigned as a superheated steam injection nozzle for injecting superheated steam, a catalyst layer forming agent injection nozzle for injecting superheated steam of a catalyst layer forming agent, and a functional layer forming agent injection nozzle for injecting a functional layer forming agent. These nozzles may be integrally moved with respect to the surface layer. In this case, as described in claim 11, when the superheated steam includes the catalyst layer forming agent, the superheated steam is held using a hermetically sealed container that holds the superheated steam at a constant pressure and a constant temperature. You may make it inject from a vapor | steam injection nozzle and make it contact a base material.
By doing in this way, contact of superheated steam, formation of a catalyst layer, and formation of functionality can be performed only by passing the plurality of injection nozzles.

As the base material layer, metals such as Be, Mg, Al, Ti, Fe, Co, Ni, Cu, Zn, Mo, Rh, Pd, Ag, Sn, Sb, W, Ir, Pt, Au, Pb, Bi Or it can be set as either the alloy containing the above-mentioned metal, and the metalloid type semimetal of B * Si.
In addition, as metal ions and / or metal oxides and / or salts thereof used for forming a protective layer, a sacrificial anticorrosive layer, etc., in particular, chromium, zinc, titanium, aluminum, tin, bismuth, calcium, magnesium, cerium or There may be mentioned at least one selected from molybdenum.
The catalyst layer forming agent is gallic acid, pyrogallol, tannic acid, citric acid, malic acid, lactic acid, tartaric acid, glycolic acid, glyceric acid, oxyvaleric acid, salicylic acid, benzoic acid, mandelic acid, oxalic acid, malonic acid. And an aqueous solution containing at least one selected from succinic acid, glutaric acid, adipic acid, maleic acid or phthalic acid, or an alkali metal salt or ammonium salt thereof, or an alkali metal salt or ammonium salt of EDTA. .

  In the present invention, the term “contact” means that the various aqueous solutions and superheated steam touch the surface layer of the base material layer, such as coating, immersion, jetting of superheated steam, and exposure in a superheated steam atmosphere. The method is not limited.

  In the present invention, the metal ions and metal oxides which are doping metal molecules include beryllium, manganese, barium, aluminum, boron, silicon, titanium, chromium, tungsten, magnesium, cerium, bismuth, calcium, zinc, tin, copper, and antimony. , Bismuth, cobalt, indium, nickel, molybdenum, palladium, silver, gold, platinum, zirconium, or tungsten. These doping metals added to the catalyst layer forming agent remain active in the catalyst layer forming agent and remain active in the surface layer of the substrate.

In the present invention, the catalyst layer refers to the formation of a catalyst layer including fine recesses and cracks in the surface layer of the base material, and metal ions or metal oxides that have entered the gaps between the metal molecules forming the surface layer. It is a layer formed with a component that can be formed and a surface layer of the base material layer. When used as superheated steam, it is a compound layer formed by ionic bonds between activated metal ions on the surface layer of the base material layer and catalyst layer forming molecules.
Similarly, in the present invention, the molecule of the functional layer forming agent is brought into contact with the surface layer of the base layer immediately after the superheated steam of the aqueous solution containing the catalyst layer forming agent is brought into contact with the catalyst layer forming agent. It is possible to form a functional layer that is firmly adhered to the component.
As described above, by forming the catalyst layer on the surface layer of the base material layer by the method of the present invention, it is possible to form a functional layer that is firmly adhered to the base material layer via the catalyst layer.

The apparatus for forming a functional layer on the surface layer of the base material layer of the present invention for carrying out the above method,
As described in claim 12, a superheated steam generator that generates superheated steam, and a hoop batch processing method (see FIG. 5-B) or a base material layer in the direction of movement from the upstream side toward the downstream side. A superheated steam spray nozzle for injecting superheated steam in order from the upstream side, and a catalyst for injecting superheated steam of a catalyst layer forming agent. The wrist layer forming agent injection nozzle and the functional layer forming agent injection nozzle for injecting the functional layer forming agent are assigned. By doing in this way, the functional layer firmly adhered to the base material layer can be efficiently formed in a short time.

  An apparatus for forming a functional layer for carrying out the above method includes a superheated steam generator for generating superheated steam, and a proximity of the base material layer from the upstream side to the downstream side in the moving direction. A superheated steam spray nozzle for injecting superheated steam in order from the upstream side, and a catalyst layer forming agent spray for injecting superheated steam of a catalyst layer forming agent. It is good to set it as the structure allocated as a functional layer formation agent injection nozzle which injects a nozzle and a functional layer formation agent.

  When the superheated steam contains the catalyst layer forming agent, the components of the volatile catalyst forming agent are not lost from the superheated steam in the process of forming the functional layer. In addition, when the superheated steam contains the catalyst layer forming agent, the superheated steam is preferably held at a constant pressure and a constant temperature to be sealed. In this case, the superheated steam injection nozzle can be used as an injection nozzle for the catalyst layer forming agent.

According to the functional layer forming apparatus of the present invention, for example, the upstream injection nozzle is assigned for superheated steam injection, and the downstream injection nozzle is assigned for injection of the catalyst layer forming agent. Immediately after contacting the surface layer of the material layer, the catalyst layer can be formed on the surface layer of the base layer.
Further, by disposing the functional layer forming injection nozzle on the downstream side of the catalyst layer forming agent injection nozzle or the superheated steam injection nozzle, a functional layer such as a resin coating layer is formed immediately after the superheated steam contact and the catalyst layer formation. Can be formed.
The present invention can also be suitably applied to medical instruments made of titanium or stainless steel. Invention of Claim 14 is set as the structure which is a medical instrument using the formation method of the functional layer to the metal base material layer surface layer in any one of Claims 1-11. The present invention can also be applied to electronic components such as multi-layer capacitors, coils, and circuit boards.

In the method of the present invention, a catalyst layer that is firmly bonded to the surface layer of the base material layer can be formed, whereby a functional layer is uniformly formed on the base material layer having excellent conformability through the catalyst layer. be able to. Moreover, the functional layer which adhered more firmly to the base material layer can be obtained by confining the functional layer forming molecules in the gaps of the base material layer on which the catalyst layer is formed.
The method of the present invention is effective when various functional layers are formed on the surface layer of a new base material layer, but when various functional layers are regenerated on the surface layer of the base material layer, for example, it is firmly formed on the base material layer. Even if a part of the coated film, rust (including oxide film) or plating layer, and a deteriorated functional layer such as a paint containing a harmful metal substance remain, various functional layers are adhered to it with high adhesion. There is also an effect that it can be formed.

Therefore, it is possible to simplify the work of forming the functional layer, reduce the work burden on the worker, shorten the work time and the cost of forming the functional layer, and Automation of layer formation is also possible. In addition, since a new functional layer can be formed without removing the functional layer deteriorated by the conventional method using a physical polishing method or the like, it is advantageous in terms of environment and health of workers.
Furthermore, a steam ejector and a plurality of injection nozzles are arranged in parallel, and a superheated steam injection nozzle and catalyst using an aqueous solution selected from an acidic aqueous solution and water and an alkaline aqueous solution according to the base material composition from the upstream side in the moving direction. By using a layer forming agent injection nozzle and a functional layer forming nozzle or a superheated steam injection nozzle and a functional layer forming nozzle containing a catalyst layer forming agent, the base material layer can be moved by a single movement operation of the combined injection nozzle. A strong functional layer can be formed on the surface layer.

It is the schematic for demonstrating the effect | action and conditions of a superheated steam used for this invention. It is the schematic of the formation method of the functional layer concerning 1st embodiment of this invention. It is the schematic of the formation method of the functional layer concerning 2nd embodiment of this invention. It is the schematic of the formation method of the functional layer concerning 3rd embodiment of this invention. It is the schematic explaining the formation apparatus of the functional layer used for the method of this invention. It is process drawing explaining the concept of the method of this invention. It is an enlarged photograph of the crystal structure which forms a base material layer surface layer. The state before the process of the base material layer of a cold rolled steel plate (SPCC) is shown, (a) is an electron micrograph of a surface layer, (b) is the qualitative analysis result of the element in the surface layer of (a), (c) Shows the quantitative analysis results on the surface layer of (a). It shows the state after processing of the base material layer when a catalyst layer forming agent containing zinc ions is used, (a) is an electron micrograph of the surface layer, (b) is a qualitative element in the surface layer of (a) The analysis results, (c), show the quantitative analysis results on the surface layer of (a). It shows the state after treatment when a catalyst layer forming agent containing silver ions is used, (a) is an electron micrograph of the surface layer, (b) is a result of qualitative analysis of elements in the surface layer of (a), ( c) shows the quantitative analysis results on the surface layer of (a). It shows the microphotograph before and after the superheated steam contact in the surface layer of each base material layer, and the quantitative analysis result according to the example of the present invention, and (a) shows the case of SUS304, (b) shows the Cu. Shows the case. It shows the microphotograph before superheated steam contact in the surface layer of each base material layer, and after contact, and a quantitative analysis result concerning an example of the present invention, (a) shows the case of Al, (b) shows SPCC. Shows the case. It is a photograph which shows the state before and behind removing the stain | pollution | contamination of the titanium material which concerns on Example 4 of this invention, and is used for a medical instrument. It is a photograph which shows the state before and behind removing the stain | pollution | contamination of the titanium material which concerns on Example 4 of this invention, and is used for another medical instrument.

DESCRIPTION OF SYMBOLS 1 Base material layer 1a Surface layer 2 Rust 3 Functional layer 4 Catalyst layer 5 Chamber or area | region 6 Conveyor S Surface layers, such as equipment layers H Superheated steam W Base material

Preferred embodiments of the present invention will be described below with reference to the drawings.
[First embodiment]
In the method for forming a functional layer of the present invention according to the first embodiment, as shown in FIG. 6 (i), after contacting superheated steam with the surface layer of the base material layer, the catalyst layer forming agent is contacted. A functional layer will be formed later.

[Base material layer]
As the base material layer to which the present invention can be applied, Be, Mg, Al, Ti, Fe, Co, Ni, Cu, Zn, Mo, Rh, Pd, Ag, Sn, Sb, W, Ir, Pt, Au, Examples thereof include Pb / Bi metals or alloys containing the aforementioned metals, glass, quartz, ceramic, concrete and concrete secondary products, wood products having holes and voids, and resins and resin-formed products. Examples of the resin include polyimide, polyamideimide, polyesterimide, polyetherimide, polyimide hydantoin-modified polyester, formal, polyurethane, polyester, polyvinyl formal, epoxy resin, phenol resin, polyhydantoin, polybenzimidazole (PBI), polypropylene, and urethane. And a thermosetting resin containing at least one selected from the group consisting of silicon.
[Functional layer]
The functional layer formed on the base material layer may be any layer that exhibits various functions such as rust prevention, corrosion prevention, protection, water permeability suppression, decoration, and weight reduction of the base material layer. The metal or resin that forms the material layer can be used as it is as the functional layer.

[Superheated steam]
The conditions of the superheated steam used in the present invention will be described with reference to FIG.
In the present invention, the superheated steam brought into contact with the base material layer has an action as shown in FIG.
In FIG. 1, white circles indicated by a symbol M <b> 1 are metal atoms or metal molecules that form the surface layer of the base material layer. A black circle indicated by a symbol M2 is a molecule that forms a new catalyst layer.

In the initial state, as shown in FIG. 1 (a), the gap between metal atoms or metal molecules (hereinafter referred to as “molecule M1” for convenience of explanation) forming the base layer is closed. By bringing the superheated steam H into contact with the molecules M1, M1,..., The gap between the molecules M1, M1,... Expands as shown in FIG. It will be ready for acceptance.
That is, the temperature of the superheated steam H and the discharge pressure are such that the gap between the molecules M1, M1,... Is until the catalyst layer forming molecules M2, M2,. Although the temperature is expanded and spread, it varies depending on the types of the catalyst layer forming molecule M2 and the molecule M1, but it can be obtained by experiments or the like.

  By bringing a catalyst layer forming agent containing a doping element into contact with the base material surface molecules M1, M1,..., Whose gaps are expanded until the molecules M2, M2,. As shown, the catalyst layer forming molecules M2, M2,... Containing the doping element enter between the molecules M1, M1,. In this state, when the gap between the molecules M1, M1,... Is restored by cooling or the like, as shown in FIG. M2... Is confined or sandwiched, and the catalyst layer forming molecules M2, M2... That are confined or sandwiched in the surface layer or inside of the molecules M1, M1. , M1... Are ionically bonded to the catalyst layer forming molecules M2, M2,... On the outer side of M1,.

FIG. 8 shows a state before processing of the base layer of the cold rolled steel plate (SPCC), and FIGS. 9 and 10 show a state after processing of the base layer of FIG. FIG. 10 shows a catalyst layer forming agent containing silver ions. FIG. 10 shows a catalyst layer forming agent containing silver ions. 8, 9, and 10, (a) is an electron micrograph of the surface layer, (b) is a qualitative analysis result of the element in the surface layer of (a), and (c) is a quantitative analysis result in the surface layer of (a). Show.
The state of the surface layer was measured and analyzed with an energy dispersive X-ray analyzer AZtecOne of a TM3030 tabletop microscope Miniscope manufactured by Hitachi High-Technologies Corporation.

In the treatment of FIG. 9, a catalyst layer forming agent containing 5% by weight of zinc ions is used in acidic electrolyzed water (PH4.0) containing 4% by weight of pyrogallol, and this catalyst layer forming agent is discharged at an outlet temperature of 125 ±. The surface layer was contacted as superheated steam at 5 ° C. for 120 seconds.
In the process of FIG. 10, a catalyst layer forming agent containing 5% by weight of silver ions is used in acidic electrolyzed water (PH4.0) containing 4% by weight of pyrogallol, and this catalyst layer forming agent is discharged at an outlet temperature of 125 ±. The surface layer was contacted as superheated steam at 5 ° C. for 120 seconds.
As shown in FIGS. 9 and 10, it can be seen that a catalyst layer containing zinc and silver is formed on the surface layer.

[Aqueous solution for superheated steam]
Depending on the composition of the base material, the aqueous solution used as the superheated steam H can be either hydrochloric acid aqueous solution, fruit acid, strong electrolytic acidic aqueous solution, water (PH 5.8 or more, less than 8.6), sodium hydroxide or alkali. An alkaline aqueous solution of electrolysis may be used. In the case of an acidic aqueous solution, the pH is preferably about 3.0 to less than 1.0.
By using the acidic aqueous solution, the oxide film on the surface layer of the base material layer can be removed and the surface layer of the base material layer can be activated. On the surface layer of the base material layer thus activated, the catalyst layer forming molecules M2, M2,... And the molecules M1, M1,. it can.

[Material of catalyst layer forming agent]
The catalyst layer forming agent activates the substrate layer surface layer by bringing it into contact with the surface layer such as the substrate layer and delays oxidation of the activated substrate surface layer, and the functional layer and the substrate layer surface layer This is to make the adhesiveness uniform and strong.
As a catalyst layer forming agent capable of forming a catalyst layer, gallic acid, pyrogallol, tannic acid, citric acid, malic acid, lactic acid, tartaric acid, glycolic acid, glyceric acid, oxyvaleric acid, salicylic acid, benzoic acid, At least one selected from mandelic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid or phthalic acid, or an alkali metal salt or ammonium salt thereof, or an alkali metal salt or ammonium salt of EDTA An aqueous solution containing seeds or more can be used.
In the present invention, the surface layer modifying treatment agent described in Japanese Patent No. 5422696 by the applicant of the present application can be used as the catalyst layer forming agent.

[Doping metal]
In this embodiment, the aqueous solution containing the catalyst layer forming agent may contain metal ions and / or metal oxide doping metals (the same applies to other embodiments including the second embodiment). In this case, the mixing ratio of metal ions and / or metal oxides in the entire aqueous solution is in the range of 0.001 to 5% by weight, preferably from the viewpoints of the effect and safety, and the handleability and work environment. It is more desirable to adjust to the range of 0.05 to 3% by weight.

If the addition amount of doping metal ions and / or metal oxides is less than 0.001% by weight based on the total amount of the aqueous solution, the addition amount of metal ions and the like is too small to obtain the desired effect. Exceeding% by weight is not preferable because the doping effect is limited, so that not only is meaningless, but a film layer made of unnecessary doping metal is formed on the surface layer of the base material, and it becomes uneconomical.
Note that these metal ions and / or metal oxides may be added not only as one type but also as a mixture of two or more types.

  Specifically, the metal constituting the doping metal ion and / or metal oxide includes beryllium, tin, manganese, barium, aluminum, boron, silicon, titanium, chromium, tungsten, zinc, tin, copper, antimony, bismuth, Mention may be made of at least one selected from calcium, cobalt, indium, nickel, molybdenum, palladium, silver, gold, platinum, magnesium, cerium, zirconium or tungsten, or a mixture thereof.

[Operation of catalyst layer forming agent]
“Catalyst layer” is a metal that forms a complex with a surface layer of a substrate that has been cleaned by removing dirt (including an oxide film) by bringing a treated aqueous solution in accordance with the composition of the substrate into contact with superheated steam. By contacting a complex-forming substance containing ions, a catalyst layer that protects the active surface layer is formed.
The catalyst layer has the function of protecting the surface of the base material layer by preventing the clean base material layer from forming an oxidation-stable film, and prevents the penetration of moisture and gas into the base material layer. In addition to fulfilling the effect of preventing the progress of corrosion from the surface layer to the deep layer of the base material layer, an alloy layer, a compound layer, a mixture layer, a ceramic layer, a resin layer, a plating layer, a protective layer or a sacrificial anticorrosive layer as a functional layer The base layer and the functional layer are integrated.
When the functional layer is a protective layer or a sacrificial anticorrosive layer, the metal ions and / or metal oxides added as the protective agent or sacrificial anticorrosive include chromium, zinc, titanium, aluminum, tin, bismuth, calcium, magnesium, There may be mentioned at least one selected from cerium or molybdenum. These metal ions and / or metal oxides can form a catalyst layer on the active surface layer of the base material layer while maintaining an active state in the catalyst layer forming agent, and include a catalyst containing a protective agent and a sacrificial corrosion inhibitor. The layer can remain active for a period of time.

[First embodiment of functional layer formation]
The procedure for forming a functional layer using the base material layer, superheated steam, and catalyst layer forming agent will be described with reference to FIG.
In the initial state shown in FIG. 2A, the metal molecules forming the surface layer 1a of the base material layer 1 are in the state as shown in FIG.

When superheated steam H is brought into contact with the surface layer 1a as shown in FIG. 2B, the gaps between the molecules M1, M1,... Of the surface layer 1a are opened as shown in FIG. The moisture contained therein evaporates and becomes a dry vacuum state, and the catalyst layer forming molecules M2, M2,.
Next, the catalyst layer forming agent is brought into contact with the surface layer 1 a of the base material layer 1. As a result, as shown in FIG. 1C, the catalyst layer forming molecules M2, M2,... Enter the inside of the molecules M1, M1,. Thereafter, the surface layer with latent heat becomes the original surface layer temperature, so that the gaps between the molecules M1, M1,... Return to the original state, and as shown in FIG. 4 is formed.
Finally, as shown in FIG. 2D, the functional layer 5 is formed by bringing a functional layer forming agent into contact with the surface layer of the catalyst layer 4.

The contact of the superheated steam, catalyst layer forming agent, and functional layer forming agent with the surface layer 1a can be performed in a single step using, for example, an apparatus as shown in FIG.
That is, the apparatus main body (not shown) has a nozzle 7a for injecting superheated steam, a nozzle 7b for injecting a catalyst layer forming agent, and a nozzle 7c for injecting a functional layer forming agent. The nozzles 7a, 7b, and 7c are arranged close to each other in the order of the nozzles 7a, 7b, and 7c from the upstream side in the moving direction I with an interval therebetween. Each of the nozzles 7a, 7b, and 7c is connected to a container 8a that generates superheated steam, a container 8b that contains a catalyst layer forming agent, and a container 8c that contains a functional layer forming agent, and the respective containers 8a, 8b, Superheated steam, catalyst layer forming agent, and functional layer forming agent are supplied from 8c to nozzles 7a, 7b, and 7c. As the container 8b for storing the catalyst layer forming agent, a container that can be sealed is selected so that the main component of the catalyst layer forming agent does not evaporate.
The nozzles 7a, 7b, and 7c are moved in the direction of arrow I at a preset speed while jetting superheated steam, catalyst layer forming agent, and functional layer forming agent from each of the nozzles 7a, 7b, and 7c. By doing in this way, it becomes possible to carry out the contact of superheated steam with the surface layer 1a, formation of the catalyst layer, and then formation of the functional layer almost simultaneously.
In addition, by mounting such an apparatus on a moving body that automatically moves along the base material layer, it is possible to automate these operations.

  In addition, the superheated steam of the catalyst layer forming agent may be generated in the container 8b, and the superheated steam of the catalyst layer forming agent may be injected from the nozzle 7b, or the superheated steam of the functional layer forming agent may be generated in the container 8c, The superheated vapor of the functional layer forming agent may be jetted from the nozzle 7c.

[Second Embodiment of Functional Layer Formation]
The method of the present invention can be applied even if a deteriorated metal functional layer (such as a plating layer or a coating layer) remains on the surface layer 1a of the base material layer 1 or rusts.
For example, in the case of an iron (Fe) -based material in contact with superheated steam, it changes to a corrosion-resistant coating by changing from rust Fe (OH) 3 ⇒ Fe 3 O 4 to iron tetroxide.
In the initial state shown in FIG. 3 (a), the functional layer 3 of a deteriorated metal such as a plating layer remains partially on the surface layer 1a of the base material layer 1, and the functional layer 3 is peeled off to form the base material layer. Rust 2 is generated in a part of the exposed portion of the surface layer 1a. In the following description, the deteriorated functional layer 3, the rust 2 and the surface layer 1a are collectively referred to as “surface layer such as a base material layer” and indicated by a symbol S.

Superheated steam H is brought into contact with the surface layer S such as the base material layer as shown in FIG.
Also in this case, as in the previous embodiment, the gaps between the molecules M1, M1,... That form the functional layer 3, the rust 2, and the surface layer 1a are opened, and the catalyst layer forming agent molecules M2, M2,.・ Acceptance is possible.
Next, as shown in FIG. 3C, the catalyst layer forming agent is brought into contact with the surface layer S such as the base material layer to form the catalyst layer 4 on the surface layer S such as the base material layer.
Finally, as shown in FIG. 3D, a functional layer forming agent is brought into contact with the surface layer of the catalyst layer 4 to form a new functional layer 5.
Also in this case, the superheated steam of the catalyst layer forming agent may be injected from the nozzle 7b, or the superheated steam of the functional layer forming agent may be injected from the nozzle 7c.

  In the present invention, even if the deteriorated functional layer 3 such as the rust 2 or the plating layer that remains firmly adhered to the surface layer 1a of the base material layer 1 remains, the new functional layer 5 can be formed as it is. In addition, the new functional layer 5 formed by the method of the present invention has almost no adhesion in comparison with the conventional regenerated functional layer formed after the rust 2 and the deteriorated functional layer 3 are completely removed by polishing or the like. There was no difference.

[Third embodiment of functional layer formation]
In the first embodiment, if a solution containing a catalyst layer forming agent is used as the aqueous solution in the step of contacting the superheated steam H of FIG. 6 (i), the superheated steam contact as shown in FIG. 6 (ii) is used. The process and the catalyst layer forming process can be combined into one.
That is, as shown in FIG. 4, by bringing the superheated steam H containing the catalyst layer forming agent into contact with the surface layer S such as the base material layer, the catalyst layer 4 is attached to the surface layer S such as the base material layer in the superheated steam contact process. A new functional layer 5 can be formed by bringing the functional layer forming agent into contact with the surface layer of the catalyst layer 4.

  In the superheated steam aqueous solution containing the catalyst layer forming agent in the third embodiment, the blending ratio of the catalyst layer forming agent is adjusted in the range of 0.05 to 10% by weight with respect to the entire aqueous solution. Is desirable. Thus, if the catalyst layer forming agent is less than 0.05% by weight with respect to the entire aqueous solution, it is too small to obtain the required effect, while if it exceeds 10% by weight, it is too much to be blended. Not meaningful and not preferred.

  In the aqueous solution, a ternary system containing pyrogallol and bismuth is desirable. In this case, in the whole aqueous solution, the proportion of pyrogallol is in the range of 0.05 to 8.0% by weight, and the proportion of bismuth is 0.005 to 0.005. A range of 3% by weight is desirable.

The amount of the catalyst layer forming agent added is appropriately determined depending on the composition of the material of the base material layer 1 that is an object, and is not particularly limited. It is preferable to set it as the range of 0.01-10.0 weight% with respect to the whole, Furthermore, it is still more preferable to set it as about 0.1-5.0 weight%.
Note that these organic acids may be added by appropriately mixing not only one type but also two or more types, if desired.

[Fourth Embodiment of Functional Layer Formation]
In the fourth embodiment, as shown in FIG. 6 (iii), before the superheated steam H is brought into contact with the surface layer S such as the base material layer, an aqueous solution such as hydrochloric acid aqueous solution, fruit acid or electrolyzed water is brought into contact. The aqueous solution may be directly contacted by applying it to the surface layer S such as the base material layer, but may be contacted as superheated steam.
By contacting the acidic aqueous solution, the oxide film formed on the surface layer 1 a of the base material layer 1 can be removed. When the oxide film on the surface layer S such as the base material layer is removed using the acidic aqueous solution, the surface layer S such as the base material layer is activated, and the element ions and the catalyst of the components constituting the surface layer S such as the base material layer generated in the active surface layer The catalyst layer 3 is formed on the surface layer S such as the base material layer by combining with the layer forming agent. The same applies when an alkaline aqueous solution is used.
Thereafter, a superheated steam of a neutral aqueous solution is brought into contact with the surface layer S such as the base material layer to form a catalyst layer on the surface layer 1a, and a functional layer forming agent is brought into contact with the surface layer of the catalyst layer 4 to form a new functional layer 5 Form.

[Fifth embodiment of functional layer formation]
This fifth embodiment is a modification of the fourth embodiment. As shown in FIG. 6 (iv), the superheated steam H of the neutral aqueous solution mixed with the catalyst layer forming agent is used as the surface layer S such as the base material layer. To form the catalyst layer 3.
According to this embodiment, the process of contacting the superheated steam of the neutral aqueous solution and the contact process of the catalyst layer forming agent in the third embodiment can be combined into one, and the process is more than the process of the third embodiment. The number can be reduced.

[Other Embodiments]
In the first and fourth embodiments, as shown in FIG. 6 (v), the catalyst layer may be formed using superheated steam of an acidic aqueous solution mixed with a catalyst layer forming agent. In this case, after forming a catalyst layer, it is good to contact the superheated steam of neutral aqueous solution.
The catalyst layer can be formed not only by superheated steam but also by application or immersion. In this case, it is advisable to contact the superheated steam of the neutral aqueous solution immediately after application or immersion (see FIG. 6 (vi)). Moreover, in order to make a catalyst layer forming agent remain on a surface layer easily, it is preferable to add a viscosity imparting agent to a catalyst layer forming agent.

[Example 1]
First, as superheated steam to be brought into contact with the surface layer of the base material layer according to the present invention, SUS and copper base material and iron base material are electrolytic acidic aqueous solution (PH4.5), and aluminum base material is electrolytic alkaline aqueous solution (PH9). .2) was used.

SUS304 plate (square 50mm x t3mm, average Ra0.27, Rz1.90), copper plate (square 50mm x t2.5mm, average Ra0.37, Rz1.64), aluminum plate (square) There are four types, 50mm x t2mm, average Ra0.34, Rz2.07), and iron plate (square 50mm x t2.3mm, average Ra0.21, Rz1.28), each size and roughness (Mitutoyo) : Measured with Surf Test SJ-301).

Next, the discharge port temperature at the nozzle outlet was 125 ± 5 ° C., the discharge pressure at the nozzle outlet was 0.32 MPa, and an aqueous solution suitable for the composition of each substrate layer was contacted as superheated steam for 120 seconds, SUS304 average Ra0.33, Rz1.96), copper plate (average Ra0.82, Rz5.23), aluminum plate (average Ra0.45, Rz2.98), and iron plate (average Ra0.66, Rz4.34) In either case, the recesses and the like were expanded by removing impurities on the surface layer, and the surface layer roughness (Ra) was increased. In FIG.11 and FIG.12, the microphotograph before and after the superheated steam contact in the surface layer of each base material layer, and a quantitative analysis result are shown. 11A shows the case of SUS304, FIG. 11B shows the case of Cu, FIG. 12A shows the case of Al, and FIG. 12B shows the case of SPCC. It can be seen from the micrographs and the results of quantitative analysis that the concave portions of the surface layer of each base material layer were expanded.

After that, a catalyst layer forming agent mixed with zinc metal ions and pyrogallol aqueous solution is contacted as superheated steam for 1 minute to form a catalyst layer, and then spray resin paint (manufactured by Asahi Pen Co., Ltd .: Multipurpose spray quick-drying type) Was applied to form a functional layer. The test substrate was naturally dried at room temperature for 30 minutes after the spray resin coating was applied, and then dried in an oven at 50 ° C. for 30 minutes.
Using a forming apparatus including three nozzles 7a, 7b, and 7c as shown in FIG. 5A, superheated steam contact, catalyst layer formation, and formation of a resin coating layer as a functional layer were simultaneously performed.

As a comparative example, each test substrate was dipped in a conventional room temperature ethanol degreasing solution for 1 minute and naturally dried, and then polished with water-resistant paper file # 1000 (manufactured by Sankyo Rikagaku Co., Ltd .: trade name FUJISTAR). After the surface layer is roughened, it is immersed for 5 minutes in a paper product that has been washed with water and then naturally dried, as well as a modification treatment agent (trade name KR-S, manufactured by Hokuriku Filter Co., Ltd.) maintained at 35 ° C. Then, each of the substrates subjected to the modification treatment after ultrasonic cleaning of water → water washing → air blowing was prepared, and the spray resin paint was applied to the surface of the test substrate in the same manner as in Example 1 above. Adhesion evaluation was performed. The results are shown in Table 1.

[Adhesion evaluation 1]
Evaluation of adhesion was carried out by drying and then cutting the dried resin coating film with 5 mm length and width intervals with a cutter to form a total of 100 squares in 10 rows.
Adhesive tape (manufactured by Nichiban Co., Ltd .: trade name Cellotape (registered trademark) CT1535) is applied to the resin coating surface of the test substrate, and after rubbing with a nail several times, the test substrate and tape are at an angle of 60 degrees. Thus, the peel test was evaluated in a state after comparison by a cross cut test (cross cut method). The adhesion evaluation test using the cellophane tape was performed twice, and the average is shown in Table 1. The adhesion strength is represented by a score, where ９０ is 90 to 100 points, ○ is 70 to 89 points, Δ is 40 to 69 points, and × is 39 points or less. As the quality of the functional layer, ○ (70 to 89 points) or more is acceptable.

[Adhesion evaluation 2]
A dyne pen for wettability check (surface energy value evaluation test pen) manufactured by Arcotest was used. In the evaluation value, 32 mN / m indicates the wettability of the standard, and thereafter, 34, 36, 38, and 40 mN / m, which have low wettability, were used. As described above, the test substrate surface is treated as described above, the ink is linearly attached to the substrate surface, and if the ink is held for 2 seconds or more, ◯ is a uniform application, and Δ is a partial Tables 2 to 5 show the state of playing, and the state of × showing the state of playing.

As a result of the above experiment, high adhesion of the functional layer to the surface layer of the base material layer was observed in any of the examples, and the effect of the method of the present invention was confirmed.
From this, the method of forming the functional layer after the contact of the superheated steam and the catalyst layer as in the present invention significantly reduces the conventional functional layer forming process, reduces the work load, and reduces the work cost. It was confirmed that it can greatly contribute to the reduction.

[Example 2]
In this Example 2, a base metal such as tin or zinc is corroded and corroded in a conductive electrolyte solution such as seawater with respect to an iron alloy (stainless steel), thereby preventing the corrosion of the iron alloy. ”Was conducted.
The conditions of Example 2 are as follows.
(1) Substrate A SUS436L flat plate, which is an iron-based alloy material, was used. The flat plate was prepared with and without a galvanized bolt (zinc bolt) attached.
(2) Pretreatment The surface of the flat plate is formed with a thin coating of micron order with zinc phosphate for the purpose of rust prevention and coating foundation, and the one using a pretreatment agent for the purpose of surface activation. In Table 6, “CH-S” was used. The thing which did not produce | generate the said film was prepared.
(3) Base metal Zinc was used. A treating agent based on a catalyst forming agent and using zinc as a doping metal in Table 6 is denoted as “KR-Z”.
(4) Catalyst layer forming agent A catalyst layer forming agent in which an acidic solution and a pyrogallol aqueous solution were mixed was prepared. In Table 6, it was described as “KR-SH”.
(5) Formation of catalyst layer The discharge port temperature at the nozzle outlet is 125 ± 5 ° C., the discharge pressure at the nozzle outlet is 0.32 MPa, and the catalyst layer forming agent is contacted as superheated steam for 1 minute. Formed. Using a forming apparatus including the nozzles 7a and 7b as shown in FIG. 5A, a protective layer or a sacrificial anticorrosive layer as a functional layer is formed by simultaneously performing superheated steam contact, catalyst layer formation and metal film layer formation. It formed on the surface of the flat plate. It is completed by immersing the base material on which the functional layer is formed in the cationic electrodeposition coating material and applying the coating material on the surface.
The test piece obtained as described above was immersed in a salt warm water of 5% and 50 ° C., and a tape peeling test was conducted in the same manner as in Example 1 after a predetermined time. With a zinc bolt, a peel test was conducted in the vertical and horizontal directions. The results are shown in Table 6.

  It can be seen that corrosion proceeds in 5%, 50 ° C. salt water by attaching zinc bolts, which are different metals from the flat plate. In the case of plating with zinc, a good adhesion strength was obtained in all regions from 72 hours to 240 hours by forming a catalyst layer by the method of the present invention.

[Example 3]
In Example 3, a resin layer as a functional layer is formed between two flat plates, the two flat plates are bonded, and after bonding, the two flat plates are pulled parallel to the bonding surface. The adhesion strength of the resin layer to the flat plate is tested. In automobiles, airplanes, ships, and the like, metal and resin are being compounded for weight reduction, but how to integrate the resin and metal firmly is an issue. This example verifies how the adhesion strength of such a composite material can be increased by the method of the present invention. The main conditions of Example 3 are as follows.
Two substrates (50mm x 50mm) each of which was contacted with superheated steam at 80 ° C for 3 minutes were applied to the hot melt adhesive applicator Hakko melter manufactured by Hakuko Co., Ltd. and the hot melt adhesive Hakko melter manufactured by the same company. Set the stick, make the adhesive part so that the two base materials overlap 25mm ± 0.5 × 50mm ± 0.5 at the center part, sandwich it with Nabeya Co., Ltd. Reed Vise Vise ERON100, fix for 5 minutes and cool slowly It was. After 5 minutes, it was taken out from the vise, the lower 15 mm of the base material was sandwiched with the same vise, and the upper part 15 mm was fixed with an automatic vice pliers manufactured by GGISKE. The fixed automatic vice pliers were pulled parallel to the adhesive surface, and the tensile force when the two substrates broke was measured. In order to measure the tensile force, a digital force gauge manufactured by A & D Co., Ltd. was attached to the automatic vice pliers. The maximum value of the force gauge has an upper limit of 50N. The used base material kept the base material warming state to 30 degree | times or more using the high temperature apparatus. The adhesive was kept in a minimum range and a weight range of 0.06 to 0.08 g was applied, and pressure was applied for 10 seconds after contact with the substrate. The treatment process was a room temperature with a liquid temperature of 20 ° ± 2 and the treatment time was 3 minutes.

[Preprocessing conditions]
The following solutions A to G were used as superheated steam with a temperature of 80 degrees when contacting the substrate.
A: Pure water B: Sodium chloride solution of PH 0.3-5 C: Hydrochloric acid aqueous solution of PH 0.1-4
D: Sodium hydroxide aqueous solution of PH 9-15 E: Sulfuric acid aqueous solution of PH 0.1-4
F: Phosphoric acid aqueous solution with PH 0.1 to 5 G: Nitric acid aqueous solution with PH: 0.1 to 4 [Types of catalyst layer forming agent]
1: pyrogallol (0.4% by weight) + sulfuric acid (5% by weight) + water (remainder)
2: Pyrogallol (0.02 wt%) + sulfuric acid (0.2 wt%) + hydrochloric acid (2 wt%) + water (remainder)
3: Pyrogallol (4% by weight) + sulfuric acid (0.3% by weight) + water (remainder)
4: Sodium chloride (12% by weight) + phosphoric acid (1.5% by weight) + water (remainder)
5: pyrogallol (0.91% by weight) + sodium fluoride (0.07% by weight) + nitric acid (0.4% by weight)
6: Salmon tannin (0.5 wt%) + carbon (carbon nanotube 1 wt%)
[Doping metal]
(Metal oxide and ions added to catalyst layer forming agent)
I: Zinc
II: Aluminum
III: Tin
IV: Bismuth V: Molybdenum VI: Ferric oxide (Bengara)

  It was allowed to stand at room temperature of 25 ° C. for 15 minutes, and after resin application (Hot Melt manufactured by Hakuko Co., Ltd.), it was left to cool for 30 minutes to confirm adhesion. The evaluation is as follows. (X) if not closely contacted, (△) if the contact strength is 1N to 30N (Newton) or less, (◯) if the contact strength is 31N to 50N or less, and (◎) if the contact strength is too strong to be measured. did. Conditions that cannot be processed are indicated by-.

"Use test substrate"
1 SUS plate: thickness 1.2mm x width 25mm x length 70mm: surface roughness Ra0.36; Ry2.52 (untreated)
2 SUS plate: The same base material is roughened with # 1000 polishing paper: surface roughness Ra0.38; Ry2.72
3 SUS plate: hydrochloric acid etching of the same substrate as above, roughening: surface roughness Ra0.43; Ry3.13
4 Aluminum plate: thickness 0.5mm x width 25mm x length 70mm: surface roughness Ra0.39; Ry2.60 (untreated)
5 Aluminum plate: Roughening the same base material with # 1000 abrasive paper: Surface roughness Ra0.53; Ry3.97
6 Aluminum plate: Caustic etching of the same substrate as above, roughening: Surface roughness Ra0.43; Ry2.82
7 Copper plate: thickness 1.2mm x width 25mm x height 70mm: Ra0.53; Ry3.97
8 Copper plate: Roughening the base material with # 1000 abrasive paper: Surface roughness Ra0.53; Ry3.97
9 Copper plate: Etching base material with hydrochloric acid to roughen it: Surface roughness Ra0.48; Ry4.13
10 Titanium plate: Thickness 1 mm x width 25 mm x length 70 mm: surface roughness Ra0.29; Ry1.58 (untreated)
11 Titanium plate: Roughening the base material with # 1000 abrasive paper: Surface roughness Ra0.36; Ry1.72
12 Titanium plate: Etching base material with hydrochloric acid to roughen it: Surface roughness Ra0.33; Ry1.66
13 Wood board: Thickness 30mm × Width 100mm × Length 1700mm: Ra5.11; Ry30.6
14 Wood board: Roughening the base material with # 1000 abrasive paper: Surface roughness Ra5.62; Ry4.5
15 Wood board: Etching base material with hydrochloric acid to roughen it: Surface roughness Ra5.57; Ry4.53
16 Stone board: 30mm thick x 100mm wide x 1700mm long: Ra7.97; Ry42.93
17 Stone board: Same as above, roughened with # 1000 abrasive paper: Surface roughness Ra7.62; Ry43.5
18 Stone board: Etching base material with hydrochloric acid to roughen it: Surface roughness Ra5.57; Ry4.53
19 ABS: Thickness 1mm x Width 50mm x Length 50mm: Ra0.36; Ry2.6
20 ABS: Same as above, roughened with # 1000 polishing paper: surface roughness Ra0.4; Ry2.67
21 PP: Thickness 1mm x Width 50mm x Length 50mm: Ra0.34; Ry2.28
22 PP: Roughening the base material with # 1000 abrasive paper: Surface roughness Ra0.41; Ry2.91
23 Concrete board (surface roughness cannot be measured due to overrange)

Each base material has an average roughness measured twice using a surf test SJ-301 manufactured by Mitutoyo Corporation.
In addition, a hole of about 1.2 mmφ was made at one end of the prepared test piece so that it could be suspended by a stainless steel wire of φ1.0 mm.
Set each of the two substrates (50mm x 50mm) treated with the modified treatment solution to the Hakoko melter manufactured by Hakuko Co., Ltd. An adhesive part was formed so that the base material overlaps 25 mm ± 0.5 × 50 mm ± 0.5 at the center part, and sandwiched between lead type vise vise ERON100 manufactured by Nabeya Co., Ltd., fixed for 5 minutes, and slowly cooled. After 5 minutes, it was taken out from the vise, the lower 15 mm of the base material was sandwiched with the same vise, and the upper part 15 mm was fixed with an automatic vice pliers manufactured by GGISKE. The fixed automatic vice pliers were pulled parallel to the adhesive surface, and the tensile force when the two substrates broke was measured. In order to measure the tensile force, a digital force gauge manufactured by A & D Co., Ltd. was attached to the automatic vice pliers. The results are shown in Table 7.

[Processing conditions]
Base material warming: Adhesive that keeps the base material warmed to 30 ° C or higher using a high-temperature device: A process that applies pressure for 10 seconds after contact with the base material in a weight range of 0.06 to 0.08 g with a minimum range : Processing time 3 minutes

[Example 4]
In Example 4, the titanium material (pure titanium, β titanium, and nickel titanium (NiTi) alloy) used for medical instruments and the like was verified for the effect of removing dirt such as an oxide film.
[Preprocessing conditions]
The following solutions A to V were used as superheated steam at a temperature of 80 degrees when contacting the substrate.
A: Nitric acid 0.1 to 10% by weight B: Nitric acid 11 to 20% by weight C: Nitric acid 21 to 30% by weight D: Nitric acid 31% by weight or more E: Sulfuric acid 0.1 to 10% by weight F: Sulfuric acid 11 to 20% by weight G: Sulfuric acid 21 wt% or more H: hydrochloric acid 0.1 to 10 wt%
I: Hydrochloric acid 11-20% by weight J: Hydrochloric acid 21% by weight or more K: Phosphoric acid 0.1-10% by weight
L: Phosphoric acid 11-20% by weight N: Phosphoric acid 21-30% by weight M: Phosphoric acid 31% by weight or more
O: Hydrofluoric acid 0.1 to 4% by weight P: Hydrofluoric acid 5 to 10% by weight
Q: Acidic ammonium fluoride 0.1-4% by weight R: Acidic ammonium fluoride 5-10% by weight
S: Neutral ammonium fluoride 0.1 to 4% by weight T: Neutral ammonium fluoride 5 to 10% by weight
U: Sodium fluoride 0.1 to 4% by weight V: Sodium fluoride 5 to 10% by weight

The results of Example 4 are shown in Table 8.
FIGS. 13 and 14 show the comparison results before and after the treatment when the NO34 treatment agent in Table 8 is used for different medical devices. (A) shows the state before the treatment, and (b) shows the state before the treatment. It is a photograph which shows the state after a process.

Evaluation criteria

Although preferred embodiments of the present invention have been described, the present invention can be implemented in various other forms without departing from the spirit or main features thereof.
For this reason, the above-described embodiment is merely an example in all respects and should not be interpreted in a limited manner. The scope of the present invention is indicated by the claims, and is not restricted by the text of the specification. Further, all modifications and changes belonging to the equivalent scope of the claims are within the scope of the present invention.
For example, in the above description, the case where the gaps between the molecules forming the surface layer are temporarily expanded has been described as an example, but a dent or a crack formed in the surface layer may be temporarily expanded. .

  In the present invention, a resin coating or other coating layer is formed or re-formed on the surface layer of a structure that is used as a member composed of iron-based main elements that have been shared over time as well as new steel structures and concrete structures. In addition to being able to be used suitably when forming, it functions when forming functional layers on the surface of automobiles, railway vehicles, ships and other large industrial machines, and on the surface of small devices such as medical devices and electronic parts. It can also be suitably used when forming a layer.

Claims (14)

A step of bringing superheated steam into contact with the surface layer of the metal substrate layer, and temporarily expanding fine dents, cracks, intermolecular or interatomic spaces in the surface layer;
Contacting a catalyst layer-forming agent containing a catalyst layer-forming molecule with the surface layer, allowing the catalyst layer-forming molecule to invade the gap and bonding with the substrate surface layer to form a catalyst layer;
Forming a functional layer on at least a part of the surface layer of the catalyst layer;
A method for forming a functional layer on the surface of a metal base material layer, comprising:   The surface layer of the metal base material layer is activated by bringing superheated steam into contact therewith, and the activated surface layer and the catalyst layer-forming molecule are combined. A method for forming a functional layer on the surface of a metal base material layer.   The functional layer is an alloy layer, a compound layer, a mixture layer, a ceramic layer, a resin layer, a plating layer, or a protective layer. Forming method.   The method for forming a functional layer on the surface layer of a metal substrate layer according to any one of claims 1 to 3, wherein a viscosity imparting agent is added to the catalyst layer forming agent.   The method for forming a functional layer on the metal base material layer surface layer according to any one of claims 1 to 4, wherein superheated steam is contacted after contacting the catalyst layer forming agent with the surface layer.   The said superheated steam contains the said catalyst layer formation agent, and the process which makes the said superheated steam contact and the process of forming a catalyst layer in the surface layer of the said base material layer are performed simultaneously. The method for forming a functional layer on the surface layer of the metal substrate layer according to any one of the above.   The method for forming a functional layer on a surface layer of a substrate according to any one of claims 1 to 6, wherein the catalyst layer forming agent contains a doping metal molecule.   The method for forming a functional layer on the surface of the metal substrate layer according to any one of claims 1 to 7, wherein the superheated steam is any one of an acidic aqueous solution, water, and an alkaline aqueous solution.   The metal group according to claim 1, further comprising a step of bringing a neutral aqueous solution or a superheated vapor of the neutral aqueous solution into contact with the surface layer after the acidic aqueous solution is brought into contact with the surface layer. A method for forming a functional layer on the surface layer of a material layer. Prepare a superheated steam generator that generates superheated steam, and a plurality of injection nozzles arranged close to the base material layer from the upstream side to the downstream side in the moving direction, and in order from the upstream side, the injection nozzles, Assigned as a superheated steam injection nozzle for injecting superheated steam, a catalyst layer forming agent injection nozzle for injecting superheated steam of a catalyst layer forming agent, and a functional layer forming agent injection nozzle for injecting a functional layer forming agent,
The method for forming a functional layer on the surface layer of the metal substrate layer according to any one of claims 1 to 9.   In the case where the superheated steam contains the catalyst layer forming agent, the superheated steam is held at a constant pressure and a constant temperature to be sealed and sealed from the superheated steam spray nozzle to the metal substrate. The method for forming a functional layer on the surface layer of the metal base layer according to claim 10, wherein contact is made. A forming apparatus for a method for forming a functional layer on a surface layer of a metal base material layer according to claim 10 or 11,
A superheated steam generating section for generating superheated steam; and a plurality of spray nozzles arranged close to the metal base material layer from the upstream side to the downstream side in the moving direction, and the spray nozzles from the upstream side In order, the superheated steam injection nozzle for injecting superheated steam, the catalyst layer forming agent injection nozzle for injecting the superheated steam of the catalyst layer forming agent, and the functional layer forming agent injection nozzle for injecting the functional layer forming agent, An apparatus for forming a functional layer on a surface layer of a metal base layer.   When the superheated steam contains the catalyst layer forming agent, the superheated steam is held at a constant pressure and a constant temperature so as to be sealed, and the superheated steam injection nozzle is connected to the catalyst layer forming agent injection nozzle. The apparatus for forming a functional layer on the surface layer of the metal base layer according to claim 12, wherein A medical device in which a functional layer is formed on the surface layer of the metal base material layer by the method according to claim 1.