JP2008260985A - Composite material and manufacturing method therefor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composite material which is obtained by chemical-conversion-treating a solid material having a plated film of a Ni-P alloy thereon, does not show coloring or shows little coloring due to the chemical conversion treatment, and has superior corrosion resistance and decoloration resistance. <P>SOLUTION: This method for manufacturing the composite material comprises the steps of: chemical-conversion-treating the plated layer of the Ni-P alloy formed on a substrate, by using chemical conversion treatment liquid including main metallic elements comprising Zr and/or Ti and a halogen element and having a pH controlled to 2.0 to 6.0; and cleaning the substrate with water. Thus formed chemical conversion coating layer contains the main metallic elements of 1 to 30 mg/m<SP>2</SP>and the phosphor element and oxygen element of 1 to 100 mg/m<SP>2</SP>respectively. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a composite material and a method for producing the same. More specifically, the present invention has a base material made of nickel-phosphorus alloy-plated metal, plastics and ceramic material, and a non-colored high corrosion resistance chemical conversion coating. In addition, the present invention relates to a composite material having no coloration and having high corrosion resistance and high discoloration resistance and a method for producing the same.

  It is known that chromate treatment is applied as a chemical conversion treatment for the purpose of preventing corrosion and discoloration of nickel-phosphorus plating film, especially electroless nickel-phosphorus alloy plating film applied to the surface of metal materials. Yes. Hexavalent chromium is contained in this chromate treatment bath and the film formed thereby. Hexavalent chromium is harmful to the human body and its use is restricted or prohibited. For this reason, development of a chemical conversion treatment method to replace chromate treatment is desired.

Regarding the hexavalent chromium-free chemical conversion treatment for materials such as metals subjected to nickel-phosphorus alloy plating, the following documents are known.
JP-A-11-152588 JP 2003-213447 A JP 2006-9089 A JP 2005-146411 A JP 2005-194603 A JP 2005-336550 A WO2005 / 103080 A2 WO03 / 074761 A1 JP 2006-328501 A

  Among the hexavalent chromium-free chemical conversion treatment agents, those containing trivalent chromium are disclosed in Patent Document 1 as a treatment liquid containing trivalent chromium, phosphate ions and nitrate ions. A treatment liquid containing trivalent chromium and inorganic acid ions such as nitric acid is disclosed. Patent Document 3 discloses a treatment liquid containing trivalent chromium and phosphorus oxyacid ions such as phosphate ions. Is disclosed.

  As a treatment liquid not containing chromium, Patent Document 4 discloses a treatment agent containing a molybdic acid compound, a tungstic acid compound, a phosphoric acid compound, a sulfuric acid compound, and a silicic acid compound. It is disclosed that a protective film containing oxygen, silicon, nickel, and phosphorus can be formed on the nickel film, and that molybdenum and / or tungsten may be further contained. Patent Document 5 discloses a surface treatment solution containing tungstic acid and / or a salt thereof, phosphoric acid and / or a salt thereof, whereby nickel tungstate and nickel phosphate are formed on the nickel film or nickel alloy film. It is disclosed to form an insoluble film containing. Patent Document 6 discloses that one surface selected from the group consisting of vinylamine, allylamine, allylamine salt, diallylamine, diallylamine salt and diallylammonium salt on a surface containing a metal such as aluminum, magnesium, cobalt, zinc, nickel, and iron. It is described that a metal surface treatment agent containing a polymer containing the above monomer as a constituent monomer is brought into contact, washed with water or hot water as necessary, and dried to form a corrosion-resistant, discoloration-resistant polymer film. Has been. However, the protective film formed with the trivalent chromium-containing treatment agent and the non-chromium-containing treatment agent is unsatisfactory in terms of corrosion resistance and discoloration resistance as compared with the chromate film.

Zirconium-based chemical conversion treatment agents and titanium-based chemical conversion treatment agents are known as chromium-free chemical conversion treatment agents used for steel materials, galvanized metal materials, and aluminum or aluminum alloy materials. Patent Document 7 discloses a surface treatment agent for a metal material containing iron or zinc containing a compound containing one or more elements selected from titanium, zirconium, hafnium and silicon, and a fluorine-containing compound serving as a supply source of HF. It is disclosed.
Patent Document 8 discloses a compound containing one or more elements selected from hafnium, titanium, zirconium, and silicon as a surface treatment agent for aluminum, aluminum alloy, magnesium, or magnesium alloy, a fluorine-containing compound, and alkaline earth. A treatment liquid containing at least one metal ion selected from the group of similar metals and nitrate ion is disclosed. However, these treatment solutions are still not fully satisfactory in the effect of improving corrosion resistance and discoloration resistance when they are used for nickel-phosphorus alloy plated metal materials.

  There has also been known an attempt to further add trivalent chromium to the zirconium-based treatment liquid or the titanium-based treatment liquid, thereby further improving the corrosion resistance. Patent Document 9 discloses an aqueous acidification composition containing a water-soluble trivalent chromium compound component, a water-soluble titanium or zirconium compound component, a water-soluble nitric acid compound component, a water-soluble aluminum compound component and a fluorine compound component, and, if necessary, an oxidizing agent component. A treatment liquid is disclosed, and the chemical conversion film formed on the aluminum or aluminum alloy material from the chemical treatment liquid contains trivalent chromium, titanium and / or zirconium, and has corrosion resistance, paint adhesion, and sludge prevention. Have been reported to be good.

  However, when the zirconium-based treatment liquid, the titanium-based treatment liquid and the zirconium and / or titanium-trivalent chromium mixed chemical conversion treatment liquid are applied to a nickel-phosphorus alloy plating metal material, particularly an electroless nickel-phosphorus alloy plating metal material, A problem has been found by the inventors that it causes coloration on the surface of the metal material. In addition, it is difficult to acquire and expand the use of the nickel-phosphorus alloy plating material having the colored protective coating as described above, particularly in electronic and electrical equipment.

  The present invention includes a base material made of a solid material having a nickel-phosphorus alloy plating layer, a high-corrosion resistance and a discoloration resistance formed thereon, and a chemical conversion treatment film, and is colored by chemical conversion treatment. Therefore, an object of the present invention is to provide a composite material having high corrosion resistance and high discoloration resistance and a method for producing the same.

A composite material according to the present invention includes a base material including a base made of a metal material, a plastics material, or a ceramic material, and a nickel-phosphorus alloy plating layer formed on at least one surface of the base, and a nickel-phosphorus alloy of the base A conversion coating layer formed by subjecting the plating layer to a conversion treatment, wherein the conversion coating layer is at least one main metal element selected from 1 to 30 mg / m ² of zirconium and titanium, and 1 to 100 mg. / M ² phosphorus element, and 1 to 100 mg / m ² oxygen element, having no or little coloration due to chemical conversion treatment, and having high corrosion resistance and high discoloration resistance.
In the composite material of the present invention, the base material is preferably selected from a metal material, a plastics material, and a ceramic material.
In the composite material of the present invention, it is preferable that the nickel-phosphorus alloy plating layer formed on the base contains phosphorus in a content of 0.05 to ²⁰ g / m ² .
In the composite material of the present invention, the atomic ratio P / (P + O) of the amount of phosphorus (P) contained in the chemical conversion film to the total amount of phosphorus and oxygen (P + O) is in the range of 0.01 to 0.25. It is preferable that it exists in.
In the composite material of the present invention, it is preferable that phosphorus contained in the chemical conversion film exists as at least one compound selected from phosphate and phosphite.
In the composite material of the present invention, it is preferable that the chemical conversion film further contains 1 to 30 mg / m ² of a first additional metal element made of trivalent chromium.
In the composite material of the present invention, it is preferable that the chemical conversion film further contains 1 to 30 mg / m ² of a second additional metal element made of at least one selected from tungsten, molybdenum, vanadium and cerium.
The method for producing a composite material according to the present invention is the above-mentioned nickel-phosphorus alloy of a base material including a base made of a metal material, a plastics material or a ceramic material, and a nickel-phosphorus alloy plating layer formed on at least one surface thereof At least a part of the surface of the plating layer is made of at least one selected from zirconium and titanium, the main metal element having a concentration of 1 to 5000 ppm, and at least one selected from fluorine, chlorine, bromine and iodine, A chemical conversion treatment solution containing a halogen element having a concentration of 1 to 10,000 ppm and having a pH of 2.0 to 6.0 is contacted, whereby at least one selected from 1 to 30 mg / m ² of zirconium and titanium. a main metal element, comprising: a phosphorus element of 1 to 100 mg / m ^2, and the oxygen element of 1 to 100 mg / m ^2, no coloring by chemical conversion treatment Less, to form a conversion coating layer having a high corrosion resistance and tarnish resistance, is the resulting conversion coating layer characterized in that the washing with water.
In the method for producing a composite material of the present invention, in the preparation of the chemical conversion treatment liquid, the main metal element is a hydrated oxide thereof, or a fluoride, chloride, oxychloride, bromide, iodide, or fluorine-containing acid. It is preferably used in the form of a salt.
In the method for producing a composite material of the present invention, in the preparation of the chemical conversion treatment solution, the halogen element is hydrochloric acid, hydrofluoric acid, hydroiodic acid, hydrobromic acid, or a chloride or fluoride of the main metal element. It is preferably used in the form of a fluoride, bromide or iodide or a salt of a fluorine-containing acid.
In the method for producing a composite material of the present invention, it is preferable that the chemical conversion treatment liquid further contains a trivalent chromium element as a first additional metal element.
In the manufacturing method of the composite material of this invention, it is preferable that the density | concentration of the trivalent chromium element in the said chemical conversion liquid is 1-5000 ppm.
In the method for producing a composite material of the present invention, in the preparation of the chemical conversion treatment liquid, the trivalent chromium element is in the form of a hydrated oxide, fluoride, chloride, bromide, iodide, or a salt of a fluorine-containing acid. Is preferably used.
In the method for producing a composite material of the present invention, the chemical conversion treatment liquid preferably contains a second additional metal element composed of at least one element selected from tungsten, molybdenum, vanadium and cerium.
In the method for producing a composite material of the present invention, the concentration of the second additional metal element in the chemical conversion treatment liquid is preferably 1 to 5000 ppm.
In the method for producing a composite material of the present invention, in the preparation of the chemical conversion treatment solution, the second additional metal element is a hydrated oxide, fluoride, chloride, bromide, iodide, or a salt of a fluorine-containing acid. It is preferably used in the form.
In the method for producing a composite material according to the present invention, when the substrate is an aluminum-containing metal material, the substrate is subjected to the nickel-phosphorus alloy plating treatment and water washing, and before the chemical conversion treatment. Further, contacting the nickel-phosphorus alloy plating substrate with hot water having a temperature of 50 ° C. or higher, or contacting the hot water having a temperature of 50 ° C. or higher with the composite material obtained by the chemical conversion treatment and the water washing. It is preferable to include.

  The composite material of the present invention includes a metal material, a plastics material, or a ceramic material having a nickel-phosphorus alloy plating layer as a base material. The chemical conversion film formed thereon by chemical conversion treatment is obtained by combining the obtained composite material. It can impart high corrosion resistance and discoloration resistance to it with little or no coloring, and the method of the present invention makes it possible to easily and efficiently produce the composite material.

  The solid material used as the substrate of the composite material of the present invention may be either a conductive solid material or a non-conductive solid material, and there is no limitation on the shape and size thereof. In general, base materials are metal materials such as iron, copper, and aluminum, and alloys thereof, plastics materials (eg, polyethylene, polypropylene, polyacetal, polyamide, polycarbonate, polysulfone, polyphenylene sulfide, polyether ether ketone, PET resin, ABS) Resin, etc.) and ceramic materials (including glass materials, for example, silicate glass, alumina, silicon nitride, silicon carbide, etc.) can be selected.

In the composite material of the present invention, the nickel-phosphorus alloy plating layer formed on the substrate can be formed by either an electroless plating method or an electrolytic plating method. As a nickel-phosphorus alloy plating bath, as a nickel supply source, for example, one or more kinds of nickel sulfate, nickel chloride, nickel carbonate, nickel hypophosphite, and the like, as a phosphorus supply source, for example, hypophosphite, An aqueous treatment liquid containing one or more types such as phosphite can be used. The thickness of the plating layer can be appropriately set as desired, but generally it is preferably about 0.5 to 20 μm, and the phosphorus content is 0.05 to 20 g / m ^2. preferable. May occur such a disadvantage that the phosphorus content in the coating layer can not be obtained a uniform plating layer is less than 0.05 g / m ^2, also plated layer it more than 20 g / m ² is practically It can be difficult to produce.

The composite material of the present invention is obtained by subjecting a substrate made of a solid material, a substrate having a nickel-phosphorus alloy plating layer formed on at least one surface thereof, and a chemical conversion treatment on the nickel-phosphorus alloy plating layer of the substrate. The conversion coating layer is formed of 1 to 30 mg / m ² , preferably 1 to 20 mg / m ² of at least one main metal selected from zirconium and titanium. Elemental, 1 to 100 mg / m ² , preferably 1 to 50 mg / m ² phosphorus element, and 1 to 100 mg / m ² , preferably 1 to 50 mg / m ² oxygen, by chemical conversion treatment It has no or little coloration and has high corrosion resistance and high discoloration resistance.

When the content of the main metal element (Zr and / or Ti) in the chemical conversion coating layer is less than 1 mg / m ² , the amount of chemical conversion coating obtained is insufficient, and the corrosion resistance and discoloration resistance are insufficient. become. On the other hand, if it exceeds 30 mg / m ² , the amount of chemical conversion film to be obtained becomes excessive, and coloring occurs due to light interference, resulting in high cost and economical disadvantage. On the other hand, if the phosphorus content is less than 1 mg / m ² , the amount of the resulting chemical conversion film is insufficient, and the corrosion resistance and discoloration resistance are insufficient. Moreover, when it exceeds 100 mg / m < ² >, there will be a disadvantage that coloring occurs. Further, when the oxygen content is less than 1 mg / m ² , the amount of the resulting chemical conversion film becomes insufficient, and the corrosion resistance and discoloration resistance become insufficient, and when it exceeds 100 mg / m ² , coloring occurs. This causes the inconvenience.

  In the composite material of the present invention, the atomic ratio P / (P + O) of the amount of phosphorus (P) contained in the chemical conversion film to the total amount of phosphorus and oxygen (P + O) is in the range of 0.01 to 0.25. Preferably, it exists in the range of 0.02-0.2. If the atomic ratio P / (P + O) is less than 0.01, that is, if the relative amount of phosphorus to oxygen is too small, the resulting composite material may have insufficient corrosion resistance and discoloration resistance. When the atomic ratio P / (P + O) is 0.25, phosphorus and oxygen take the form of phosphite, so the value of P / (P + O) does not exceed 0.25.

The composite material of the present invention can be produced by the method of the present invention.
In the method of the present invention, a substrate in which a nickel-phosphorus alloy plating layer is formed on one surface of a substrate made of a solid material is used as a substrate, and chemical conversion treatment is performed on at least a part of the surface of the nickel-phosphorus alloy plating layer of the substrate. The liquid is brought into contact and subjected to chemical conversion treatment. The chemical conversion treatment liquid contains at least one main metal element selected from zirconium and titanium at a concentration of 1 to 5000 ppm, preferably 5 to 1000 ppm, and is selected from fluorine, chlorine, bromine and iodine. At least one halogen element at a concentration of 1 to 10000 ppm, preferably at a concentration of 5 to 5000 ppm, and a pH of 2.0 to 6.0, preferably 2.5 to 5.5. It is what you have. The solvent of the chemical conversion treatment solution is preferably water, or may be a polar solvent compatible with water, or a mixture of water and a polar solvent.
As the polar solvent, alcohol-based, glycol ether-based, amide-based solvents and the like are used. Specifically, ethanol, methanol, 2-propanol, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, ethylene glycol monobutyl ether, formamide , Dimethylformamide, monoethanolamine, triethanolamine, N-methylpyrrolidone, tetrahydrofuran, dioxane and the like.
The contact between the chemical conversion treatment liquid and the nickel-phosphorus alloy plating layer of the substrate is preferably 20 to 80 ° C., more preferably 30 to 70 ° C., preferably 1 to 1800 seconds, more preferably 5 to 5 ° C. It is performed with a contact time of 600 seconds.

By contact with the chemical conversion treatment liquid, a chemical conversion coating layer is formed on the nickel-phosphorus alloy plating layer, and in this chemical conversion coating layer, 1 to 30 mg / m ² of the main metal element (Zr and / or Ti), 1-100 mg / m ² of phosphorus element and 1-100 mg / m ² of oxygen element are contained.
When the temperature of the chemical conversion treatment liquid is less than 20 ° C., the etching rate is low, the formation rate of the chemical conversion film having the above composition is slow, and a sufficient chemical conversion film may not be formed within a practical processing time. If it exceeds 80 ° C., the metal element in the treatment liquid is precipitated by hydrolysis, and it becomes easy to generate sludge, and the energy cost may be high, which may be economically disadvantageous. Further, if the treatment time is less than 1 second, the chemical conversion reaction is not sufficiently performed, and the formation of the chemical conversion film may be insufficient. If it exceeds 1800 seconds, the chemical reaction effect is saturated and practical. Productivity decreases.

  In the method of the present invention, the thickness of the chemical conversion coating layer formed by chemical conversion treatment is preferably 1 to 100 nm. If the thickness of the chemical conversion coating layer is less than 1 nm, the corrosion resistance and discoloration improvement effect may be unsatisfactory. If it exceeds 100 nm, the corrosion resistance and change resistance improvement effect is saturated, and the cost is reduced. There may be economic disadvantages due to the rise, and coloration may occur due to light interference.

  After the chemical conversion liquid contact is completed, the obtained chemical conversion film layer is washed with water to remove the attached chemical conversion liquid. In this water washing, washing with water at 5 to 80 ° C. is preferably performed once or twice, followed by washing with deionized water at 5 to 80 ° C. once or twice.

  The chemical conversion treatment solution used in the method of the present invention contains a main metal element and a halogen element. The main metal element for the chemical conversion treatment liquid is at least one selected from zirconium (Zr) and titanium (Ti), and can improve the corrosion resistance and discoloration resistance of the resulting composite material. In the preparation of the chemical conversion treatment liquid, the main metal element is a water-soluble compound such as a hydrated oxide, chloride, fluoride, iodide, bromide, and a salt of a fluorine-containing acid (for example, a fluorozirconium (IV) complex salt, It is preferably used in the form of fluorotitanium (III) or (IV) acid complex salt), and the content of the main metal element (Zr and / or Ti) in the chemical conversion solution is preferably 1 to 5000 ppm, Is less than 1 ppm, the resulting chemical conversion film is insufficient in corrosion resistance and / or discoloration resistance. Moreover, when it exceeds 5000 ppm, although the performance of the chemical conversion film obtained will be saturated, cost will become high and it will become economically disadvantageous.

The chemical conversion treatment liquid contains at least one halogen element selected from fluorine, chlorine, bromine and iodine, and this halogen element has an etching effect on the nickel-phosphorus alloy plating layer and substrate of the chemical conversion treatment liquid. Therefore, it is an important component for controlling the chemical reaction. Moreover, the etching effect by the halogen element does not cause coloring in the obtained composite material. The cause of coloration of the resulting composite material by chemical conversion treatment is the generation of interference colors due to the chemical conversion coating layer produced by chemical conversion treatment. Also, during the chemical conversion treatment, the nickel-phosphorus alloy plating layer has surface irregularities caused by etching. May form, which may cause coloration. In the chemical conversion solution, there is a tendency to color the chemical conversion treatment product obtained by the presence of ions of inorganic acids such as nitric acid, sulfuric acid and phosphoric acid and ions of organic acids such as acetic acid, formic acid, tartaric acid and citric acid. In particular, it has been found by the present inventors that nitrate ions form significant irregularities on the surface of the nickel-phosphorus alloy plating layer and cause coloring. The acids that generate the above color are not necessary for the method of the present invention, and they are not included in the chemical conversion solution from the beginning. The halogen element in the chemical conversion treatment liquid includes hydrofluoric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, and fluoride, chloride, bromide, and the main metal element (Zr and / or Ti), It is preferably present in the form of iodide and a salt of a fluorine-containing acid.
Content of the said halogen element in the chemical conversion liquid used for the method of this invention is 1-10000 ppm. If the content is less than 1 ppm, the etching effect on the surface of the substrate such as the nickel-phosphorus alloy plating layer becomes insufficient, and therefore the chemical conversion effect becomes insufficient. On the other hand, if the content of the halogen element exceeds 10,000 ppm, the etching effect becomes excessive and the cost becomes high, which is economically disadvantageous.

  In the method of the present invention, it is preferable that the chemical conversion solution further contains a trivalent chromium (Cr (III)) element as the first additional metal element. In the formation of a conversion coating obtained by adding trivalent chromium, the amount of metal-containing component deposited can be suppressed, and coloring due to interference colors due to excessive deposition can be prevented. In order to contain the trivalent chromium in the chemical conversion treatment liquid, a hydrated oxide of trivalent chromium, fluoride, chloride, bromide, iodide, fluorine-containing fluorochrome (III) salt, and fluorometal acid (for example, It is preferable to use a trivalent chromium salt of chromium (III) fluorozirconate. The content of the trivalent chromium element in the chemical conversion treatment liquid is preferably 1 to 5000 ppm, and more preferably 5 to 1000 ppm. If the content is less than 1 ppm, the effect of adding trivalent chromium may be insufficient, and if it exceeds 5000 ppm, the rate of cost increase for the action and effect will be excessive, which will be economically disadvantageous. There is.

  In the method of the present invention, the chemical conversion treatment liquid may contain a second additional metal element composed of one or more selected from tungsten, molybdenum, vanadium, and cerium, if necessary. Corrosion resistance and discoloration resistance can be further improved. The content of the second additional metal element in the chemical conversion solution is preferably 1 to 5000 ppm, more preferably 5 to 1000 ppm. In the preparation of the chemical conversion treatment solution, the second additional metal element is a hydrated oxide, fluoride, chloride, bromide, iodide, or fluorine-containing acid salt of each metal element (for example, a fluorotungsten (V) acid complex salt). , Fluoromolybdenum (III), (IV), (V) or (VI) acid complex salt, fluorovanadium (III), (IV) or (V) acid complex salt, etc.). If the content of the second additional metal element in the chemical conversion solution is less than 1 ppm, the effect of improving the corrosion resistance and discoloration resistance due to the addition of the second additional metal element in the resulting composite material may be insufficient. In addition, if it exceeds 5000 ppm, the cost increase rate for the obtained effect is too high, which may be economically disadvantageous.

  In the method of the present invention, the pH of the chemical conversion solution is adjusted within the range of 2.0 to 6.0, preferably within the range of 2.5 to 5.5. For this pH adjustment, a conventional pH adjuster may be used. However, in order to avoid contamination with harmful anions in the chemical conversion film of the present invention, for example, hydrofluoric acid, sodium hydroxide and aqueous ammonia are added. It is preferable to use it. When the pH of the chemical conversion solution is less than 2.0, the etching power of the chemical conversion solution on the nickel-phosphorus alloy plating layer becomes excessively strong, and the effect of forming a desired chemical conversion film is reduced. As a result, the amount of leaching is excessive, the running performance of the chemical conversion treatment becomes poor, and the degree of unevenness formation on the surface of the plating layer becomes excessive. On the other hand, if the pH value exceeds 6.0, the amount of sludge generated by the chemical conversion treatment increases, and the stability of the chemical conversion liquid becomes poor.

The formation mechanism of the chemical conversion film in the chemical conversion treatment is as follows.
In the method of the present invention, when the halogen-containing aqueous acidic chemical conversion treatment solution comes into contact with the nickel-phosphorus alloy plating layer, the nickel and phosphorus components in the plating layer in contact with the chemical conversion treatment solution (and in some cases, in the defective portion of the plating layer, Etching the substrate (metal components such as iron and aluminum in the substrate in contact with the chemical conversion treatment solution) to cause a hydrogen generation reaction, resulting in a decrease in hydrogen ion concentration and an increase in pH value in the vicinity of the plating layer. To do. On the other hand, in the chemical conversion treatment liquid, the main metal element (Zr and / or Ti) forms a complex with a halogen-containing ion generated from the halogen element-containing substance contained in the chemical conversion treatment liquid, but this increases the pH. As a result, the stability of the halogen-containing ion complex decreases.
Further, phosphorus in the plating layer is oxidized and eluted from the plating layer in contact with the chemical conversion treatment solution to generate phosphate ions and / or phosphite ions. Zr and / or Ti in the destabilized halogen-containing ion complex reacts with OH ions, phosphate ions, phosphite ions, and the like generated in the vicinity of the plating layer to form water-insoluble hydroxides. , Oxides, phosphates and / or phosphites are deposited and deposited on the surface of the plating layer.
The generation and precipitation of the coating material containing the main metal element, phosphorus element and oxygen element occurs mainly near the surface of the nickel-phosphorus alloy plating layer, but the base is a metal material (for example, aluminum, iron, etc.). In some cases, the generation proceeds on the exposed surface of the metal material substrate, and the entire surface of the base material is covered with the chemical conversion coating layer. Therefore, the chemical conversion film formed on the substrate surface is formed by a composite of the main metal (Zr and / or Ti) element hydroxide, oxide, phosphate, phosphite, etc., and has barrier properties. It is made of a high substance.

When the chemical conversion treatment liquid contains the first additional metal element (Cr (III)) and / or the second additional metal (W, Mo, V and / or Ce) element, the second additional metal is also a main metal element ( Like Zr and / or Ti), it precipitates in the form of hydroxide, oxide, phosphate and / or phosphite and is contained in the conversion coating to reinforce the barrier properties of the conversion coating layer, Corrosion resistance and discoloration resistance are further improved, but they are not colored. In this case, the content of the first and second additional metal element in the chemical conversion coating film obtained, respectively, is preferably 1 to 30 mg / m ^2, more preferably 1 to 20 mg / m ^2.
If the contents of the first and second additional metal elements in the resulting chemical conversion coating are each less than 1 mg / m ² , the corrosion resistance and discoloration resistance improving effect due to each addition may be insufficient. If it exceeds 30 mg / m ² , the thickness of the resulting chemical conversion film may be excessive, resulting in coloring due to light interference, and the production cost may be increased, which may be economically disadvantageous.

In the method of the present invention, when the substrate is an aluminum-containing metal, the nickel-phosphorus alloy plating base is applied to the substrate after the nickel-phosphorus alloy plating treatment and water washing and before the chemical conversion treatment. It is preferable to further include bringing hot water having a temperature of 50 ° C. or higher into contact with the composite material obtained by bringing the material into contact with hot water having a temperature of 50 ° C. or higher, or performing the chemical conversion treatment and washing with water. If it does in this way, the corrosion resistance of the metal composite material which uses an aluminum containing metal material as a base | substrate can be improved further.
The hot water treatment temperature at this time is 50 ° C. or higher, and is preferably closer to 100 ° C., and the purity of the water used is preferably higher. The hot water treatment time is preferably 1 to 1800 seconds, and more preferably 5 to 600 seconds. When the hot water temperature is less than 50 ° C. and when the treatment time is less than 1 second, the effect of improving the corrosion resistance is insufficient. On the other hand, when the hot water treatment time exceeds 1800 seconds, the effect is saturated and practical productivity is lowered.
As the mechanism of the above hot water treatment effect generation, an aluminum oxide (boehmite) film is formed on the exposed surface of the aluminum-containing metal substrate, which causes a sealing effect, thereby showing a barrier effect against corrosion. It is done.

The composite material of the present invention and the production method thereof will be described by the following examples.
(1) Substrates used in the following examples and comparative examples are as follows.
Aluminum plate: A5052 material, thickness: 0.5mm
Cold rolled steel sheet: SPCC material, thickness: 0.5mm
Plastics material: polypropylene plate, thickness: 0.5mm
Ceramic material: Alumina plate, thickness: 0.5mm
(2) Nickel-phosphorus alloy plating The nickel-phosphorus alloy plating agent (trademark: SEK-670, manufactured by Nihon Kanisen Co., Ltd.) is used on both the front and back surfaces of the substrate to perform electroless plating and used as a substrate. A nickel-phosphorus alloy plating metal material was produced.
Nickel - deposition of phosphorus alloy plating layer is a single-sided per 40 g / m ² of substrate, the amount of nickel and phosphorus was per side 38 g / m ² and 2 g / m ^2, respectively.

Moreover, the following measurement and evaluation were performed in the Example and the comparative example.
1. X-ray fluorescence analysis of chemical conversion film Quantitative analysis of main metal elements (Zr, Ti), first additional metal element (Cr (III)), and second additional metal element (W, Mo, V, Ce) in chemical conversion film It was carried out by a calibration curve method using a fluorescent X-ray analysis (XPF analysis) apparatus.
As for phosphorus and oxygen, the sample is subjected to ion sputtering and subjected to XPS analysis in the depth direction from the surface, and peaks derived from corrosion-resistant metal elements (Zr, Ti), phosphorus (P), and oxygen (O) in each layer. Analysis software installed in the XPS analyzer using integrated values in each layer of area intensity of (Zr: Zrd, Ti: Ti2p, O: Os, P: Pp, 132-134 eV derived from the oxidation state) Was used to calculate the atomic ratio of Zr, Ti, P, O. Based on the obtained atomic ratio and the adhesion amount of Zr and Ti, the adhesion amount of P and O, and the atomic ratio of P to the total amount of P and O (P / (O + P)) were calculated. The equipment and measurement conditions used were as follows.
(1) XRF analyzer: Model XRF-1800 (manufactured by Shimadzu Corporation)
Tube: Rh, tube voltage: 40 kV, tube current: 70 mA
Spectroscopic crystals: LiF (Ti to U, K, Ca, Sn to Cs), Ge (Cl, S, P), PET (Si, Al), TAP (Mg, F), SX-58N (C), SX -76 (N), SX-14 (O)
PR gas flow rate: 7mL / min

(2) XPS analyzer: Model ESCA-850M (manufactured by Shimadzu Corporation)
Excitation X-ray: Mg-Kα, output: 8 kV-30 mA, detection angle: 90 °

2. Evaluation of Colorlessness The color of the surface treatment film of the obtained composite material was visually observed, compared with the color before the surface treatment, and evaluated and displayed in the following three stages.
3 No change 2 Slightly colored 1 Clearly colored

3. Evaluation of corrosion resistance The surface treatment film of the obtained composite material was subjected to a neutral salt spray test of JIS H 8502 (1999), and the test was performed for 24 hours. The obtained results were evaluated and displayed in the following 7 levels.
Rating number corrosion area rate (%)
RN10 0
RN 90 Less than 0.1-0.1 RN 8 Less than 0.1-0.25 RN 7 Less than 0.25-0.5 RN 6 Less than 0.5-1.0 RN 5 Less than 1.0-2.5 RN 4 2.5 to less than 5

4). Evaluation of discoloration resistance The surface treatment film of the obtained composite material was brought into contact with an O-ring made of acrylonitrile rubber and heated at a temperature of 190 ° C. for 1 hour. The resulting color change on the surface of the composite metal material was evaluated and displayed in the following three stages in comparison with the color change of the standard sample (the substrate subjected to the chromate treatment method).
3: Almost the same as the standard sample 2: Color change is slightly larger than the standard sample 1: Color change is clearly larger than the standard sample

Example 1
The nickel-phosphorus alloy plating A5052 material (thickness: 0.5 mm) was used as a base material. Fluorozirconic acid as the main metal element component, hydrofluoric acid as the halogen element-containing component and chromium (III) fluoride as the first additional element-containing component, no nitrate ion, pH of 4 and temperature of 40 ° C A chemical conversion treatment liquid having the component composition shown in Table 1 was prepared.
The base material was immersed in the chemical conversion solution for 10 minutes, and then the chemical conversion-treated composite metal material obtained was pulled up and washed with water, washed with deionized water, and dried at a temperature of 120 ° C. for 10 minutes. No hot water treatment was applied. The analysis and evaluation results are shown in Table 2.

Example 2
In the same manner as in Example 1, a composite material was produced and analyzed and evaluated. However, the chemical conversion treatment liquid and the treatment conditions were changed as shown in Table 1.
That is, fluorotitanic acid is used as the main metal element-containing component in the chemical conversion treatment liquid, the Ti concentration is changed to 150 ppm, the amount of hydrofluoric acid used is changed to 300 ppm, and the fluorine concentration is changed to 300 ppm. The amount of chromium (III) chloride used was changed so that the Cr (III) concentration was 100 ppm, the pH of the chemical conversion solution was changed to 3, the processing temperature was changed to 60 ° C, and the processing time was changed to 5 minutes. changed.
The analysis and evaluation results are shown in Table 2.

Example 3
A composite material was produced in the same manner as in Example 1, and analyzed and evaluated. However, the composition of the chemical conversion treatment liquid and the treatment conditions were changed as shown in Table 1.
That is, fluorozirconic acid is used as the main metal element-containing component, the amount used is changed so that the Zr concentration becomes 100 ppm, and fluorotitanic acid is added, and the amount used becomes the Ti concentration of 100 ppm. And using hydrofluoric acid as the halogen element-containing component, changing the amount used so that the F concentration is 500 ppm, using chromium fluoride (III) as the first additional element-containing component, and using it The amount was changed so that the Cr (III) concentration was 100 ppm, the pH of the surface treatment solution was changed to 4.5, the treatment temperature was changed to 50 ° C., and the treatment time was changed to 5 minutes.
The analysis and evaluation results are shown in Table 2.

Example 4
A composite metal material was produced in the same manner as in Example 1 and analyzed and evaluated. However, the composition of the chemical conversion treatment liquid and the treatment conditions were changed as shown in Table 1.
In other words, the amount of hydrofluoric acid used was changed so that the F concentration was 300 ppm, chromium fluoride (III) C was not used, the pH of the chemical conversion solution was changed to 3.5, and the treatment time was Changed to 1 minute.
The analysis and evaluation results are shown in Table 2.

Example 5
A composite material was produced in the same manner as in Example 1, and analyzed and evaluated. However, a cold-rolled steel plate (SPCC) (thickness: 0.5 mm) was used as the metal substrate.
The analysis and evaluation results are shown in Table 2.

Example 6
A composite material was produced in the same manner as in Example 1, and analyzed and evaluated. However, the composition of the chemical conversion treatment liquid and the treatment conditions were changed as shown in Table 1.
That is, fluorotitanic acid is used as the main metal element-containing component, the amount used is changed so that the Ti concentration is 250 ppm, and cerium (IV) hydroxide is added as the second additional metal element-containing component. The amount was adjusted so that the Ce concentration was 100 ppm.
The analysis and evaluation results are shown in Table 2.

Example 7
A composite material was produced in the same manner as in Example 1, and analyzed and evaluated. However, the composition of the chemical conversion treatment liquid and the treatment conditions were changed as shown in Table 1.
That is, as the main metal element-containing component, fluorozirconic acid was used, the amount used was changed so that the Zr concentration was 150 ppm, the amount used of hydrofluoric acid was changed so that the F concentration was 400 ppm, Sodium tungstate (IV) is used as the second additional metal element-containing component, and the amount used is added in such an amount that the W concentration becomes 50 ppm, the pH of the chemical conversion treatment solution is changed to 4.5, and the treatment temperature is changed. Changed to 50 ° C.
The analysis and evaluation results are shown in Table 2.

Example 8
A composite material was produced in the same manner as in Example 1, and analyzed and evaluated. However, the composition of the chemical conversion treatment liquid and the treatment conditions were changed as shown in Table 1.
That is, as the main metal element-containing component, fluorotitanic acid is used, the amount used is changed so that the Ti concentration is 100 ppm, the amount used hydrofluoric acid is changed so that the F concentration is 300 ppm, The amount of chromium (III) fluoride used was changed so that the Cr (III) concentration was 200 ppm, sodium vanadate (V) was used as the second additional metal element-containing component, and the amount of V It adjusted so that it might become 200 ppm. Further, the pH of the chemical conversion treatment solution was changed to 3.5, the treatment temperature was changed to 60 ° C., and the treatment time was changed to 5 minutes.
The analysis and evaluation results are shown in Table 2.

Example 9
A composite material was produced in the same manner as in Example 1, and analyzed and evaluated. However, the composition of the chemical conversion treatment liquid and the treatment conditions were changed as shown in Table 1.
That is, as the main metal element-containing component, fluorozirconic hydrofluoric acid is used, the amount used is changed so that the Zr concentration becomes 200 ppm, and the amount used of hydrofluoric acid is changed so that the F concentration becomes 500 ppm, The amount of chromium (III) fluoride used was changed so that the Cr (III) concentration was 300 ppm, sodium molybdate (VI) was used as the second additional metal element-containing component, and the amount used was changed to the Mo concentration. However, it adjusted to the quantity used as 100 ppm, and changed the process temperature of the chemical conversion liquid to 50 degreeC.
The analysis and evaluation results are shown in Table 2.

Example 10
A composite material was produced in the same manner as in Example 1, and analyzed and evaluated. However, the composition of the surface treatment liquid and the treatment conditions were changed as shown in Table 1.
That is, as the main metal component, the amount of fluorotitanic acid used is changed so that the Ti concentration is 150 ppm, the amount of hydrofluoric acid used is changed so that the F concentration is 300 ppm, and hydrochloric acid is used. Add the amount of Cl concentration to 500ppm, change the amount of chromium (III) C used so that the Cr (III) concentration becomes 200ppm, change the pH of the surface treatment solution to 4.5, The processing temperature was changed to 50 ° C.
The analysis and evaluation results are shown in Table 2.

Example 11
A composite material was produced in the same manner as in Example 1, and analyzed and evaluated. However, the composition of the surface treatment liquid and the treatment conditions were changed as shown in Table 1.
That is, as the main metal component, fluorotitanic acid is used in an amount such that the Ti concentration is 200 ppm, the amount of hydrofluoric acid used is changed so that the F concentration is 400 ppm, and hydrobromic acid is used with a Br concentration of The amount of chromium fluoride (III) C used was changed to an amount of 300 ppm, and the Cr (III) concentration was changed to 500 ppm, and the concentration of the surface treatment solution was changed to 4.5.
The analysis and evaluation results are shown in Table 2.

Example 12
A composite material was produced in the same manner as in Example 1, and analyzed and evaluated. However, the composition of the chemical conversion treatment liquid and the treatment conditions were changed as shown in Table 1.
That is, as the main metal element-containing component, fluorozirconic acid is used, the amount used is changed so that the Zr concentration is 250 ppm, the amount used of hydrofluoric acid is changed so that the F concentration is 500 ppm, Then, hydroiodic acid was added in such an amount that the I concentration was 600 ppm, the amount of chromium (III) fluoride was changed so that the Cr (III) concentration was 300 ppm, and the pH of the chemical conversion treatment solution was changed to 3 .5, the processing temperature was changed to 60 ° C., and the processing time was changed to 5 minutes.
The analysis and evaluation results are shown in Table 2.

Example 13
A composite material was produced in the same manner as in Example 1, and analyzed and evaluated. However, after forming the chemical conversion film, washing with water, and washing with deionized water, the film was immersed in deionized water heated to 80 ° C. for 5 minutes to perform warm water treatment, pulled up, and dried at a temperature of 120 ° C. for 10 minutes.
The analysis and evaluation results are shown in Table 2.

Comparative Example 1
A composite material was produced in the same manner as in Example 1, and analyzed and evaluated. However, chemical conversion treatment solution of nitric acid NO ₃ ^- ion concentration was added in an amount to be 500 ppm.
The analysis and evaluation results are shown in Table 2.

Comparative Example 2
A composite material was produced in the same manner as in Example 1, and analyzed and evaluated. However, the composition of the chemical conversion treatment liquid and the treatment conditions were changed as shown in Table 1.
That is, the amount of hydrofluoric acid used was changed so that the F concentration was 300 ppm, chromium (III) C was not used, and the pH of the surface treatment solution was changed to 3.5. For this reason, the adhesion amount of zirconium became 50 mg / m ² .
The analysis and evaluation results are shown in Table 2.

Comparative Example 3
A composite metal material was produced in the same manner as in Example 1 and analyzed and evaluated. However, the composition of the chemical conversion treatment liquid and the treatment conditions were changed as shown in Table 1.
That is, without using the main metal element-containing component, the amount of hydrofluoric acid used was changed so that the F concentration was 300 ppm, and the amount of chromium (III) fluoride used was changed to a Cr (III) concentration of 100 ppm. The surface treatment time was changed to 5 minutes.
The analysis and evaluation results are shown in Table 2.

Comparative Example 4
In the same manner as in Example 1, a nickel-phosphorus alloy plating was applied to an aluminum plate (A5052) to prepare a base material, which was then heated to 30 ° C. with 3% potassium dichromate (K ₂ Cr (VI) ₂ O ₇ ) A chemical conversion film was formed by immersing in an aqueous solution for 5 minutes, and the resulting composite metal material was pulled up, washed with water and deionized water, and dried at a temperature of 120 ° C. for a sufficient period of time.
The obtained chromate chemical conversion treatment composite metal material was subjected to the same analysis and evaluation as in Example 1. The results are shown in Table 2.

Comparative Example 5
The nickel-phosphorus alloy plating A5052 material prepared in the same manner as in Example 1 was subjected to the same evaluation as in Example 1. The results are shown in Table 2.

Example 14
A composite material was produced in the same manner as in Example 1. However, as a base material, a polypropylene plate (thickness: 0.5 mm) was used as a plastic material instead of an aluminum plate.
Nickel - deposition of phosphorus alloy plating layer in an amount of nickel and phosphorus is per side 10 g / m ² of the substrate, respectively per one side was 9.5 g / m ² and 0.5 g / m ^2.
The analysis and evaluation results are shown in Table 2.

Example 15
A composite material was produced in the same manner as in Example 1. However, an alumina plate (thickness: 0.5 mm) was used as the ceramic material instead of the aluminum plate as the base material.
Nickel - deposition of phosphorus alloy plating layer in an amount of nickel and phosphorus is per side 16g / m ² of substrate were respectively per side 15 g / m ² and 1 g / m ^2.
The analysis and evaluation results are shown in Table 2.

As shown in Tables 1 and 2, in Comparative Example 1, a treatment liquid containing nitrate ions in addition to zirconium, trivalent chromium and fluoride ions is used. In this case, the discoloration resistance is Although it had the same performance as the chromate chromate of Comparative Example 4 using hexavalent chromium, it was confirmed that coloring was caused by the chemical conversion treatment.
In Comparative Example 2, the acidic surface treatment liquid did not contain trivalent chromium, but a treatment liquid containing zirconium and hydrofluoric acid was used, and the amount of zirconium deposited was an excess amount of 50 mg / m ² . It was confirmed that the obtained chemical conversion film was colored by light interference.
In Comparative Example 3, since the treatment liquid containing no zirconium and trivalent chromium and fluoride ions was used, coloring did not occur. However, the obtained chemical conversion film was chromium in corrosion resistance and discoloration resistance. It was confirmed that the acid chromate treatment was inferior.
In contrast to Comparative Examples 1 to 3, in Example 4, the treatment liquid containing zirconium and fluoride ions containing no nitrate ions was used and the treatment time was shortened. the amount of deposition is an appropriate amount of 10 mg / m ^2, therefore, not to be colored due to interference of light occurs, and chromic acid chromate equivalent corrosion resistance, to have a discoloration resistance was confirmed.
In Examples 1 to 3, 5, 10 to 12, 14, and 15, treatment liquids containing trivalent chromium, no nitrate ions, and containing zirconium, titanium, or halide ions are used. The obtained chemical conversion coating does not cause coloration even when treated for a long time of 10 minutes regardless of the type of the plating substrate, and is superior in corrosion resistance and discoloration resistance compared to the chromate chromate coating. confirmed.
In Examples 6-9, since at least 1 sort (s) of tungsten, molybdenum, vanadium, and cerium was contained in the process liquid, it was confirmed that the corrosion resistance of the obtained chemical conversion film has improved further.
Furthermore, in Example 13, since the immersion treatment in the treatment liquid containing zirconium, trivalent chromium, and hydrofluoric acid was combined with the hot water treatment, the obtained chemical conversion coating had a chromic acid chromate treatment. A significant improvement in corrosion resistance was observed.

  The non-colored high corrosion resistance composite material of the present invention and the production method thereof impart high corrosion resistance and discoloration resistance to a substrate having a nickel-phosphorus alloy plating layer with little or no coloration due to chemical conversion treatment. Further, the application of the nickel-phosphorus alloy plating material can be further expanded and increased.

Claims (17)

A base material including a base made of a metal material, a plastics material or a ceramic material, and a nickel-phosphorus alloy plating layer formed on at least one surface of the base, and a chemical conversion treatment on the nickel-phosphorus alloy plating layer of the base And at least one main metal element selected from 1 to 30 mg / m ² of zirconium and titanium, and 1 to 100 mg / m ² of phosphorus element, , And 1 to 100 mg / m ² of oxygen element, having no or little coloration due to chemical conversion treatment, and having high corrosion resistance and high discoloration resistance.   The composite material according to claim 2, wherein the base metal material is selected from an aluminum material, an aluminum alloy material, a steel material, and a copper alloy material. The composite material according to claim 1, wherein the nickel-phosphorus alloy plating layer formed on the substrate contains phosphorus in a content of 0.05 to ²⁰ g / m ² .   The atomic ratio P / (P + O) of the amount of phosphorus (P) contained in the chemical conversion film to the total amount of phosphorus and oxygen (P + O) is in the range of 0.01 to 0.25. 4. The composite plating material according to any one of 3 above.   The composite material according to any one of claims 1 to 4, wherein phosphorus contained in the chemical conversion coating is present as at least one compound selected from a phosphate and a phosphite. The composite material according to any one of claims 1 to 5, wherein the chemical conversion film further includes 1 to 30 mg / m ² of a first additional metal element made of trivalent chromium. The said chemical conversion film further contains 1-30 mg / m < ² > 2nd additional metal element which consists of at least 1 sort (s) chosen from tungsten, molybdenum, vanadium, and cerium. Composite material. At least a part of the surface of the nickel-phosphorus alloy plating layer of the base material including a base material made of a metal material, a plastics material, or a ceramic material and a nickel-phosphorus alloy plating layer formed on at least one surface thereof, zirconium And a main metal element having a concentration of 1 to 5000 ppm, and at least one selected from fluorine, chlorine, bromine and iodine, and containing a halogen element having a concentration of 1 to 10000 ppm And at least one main metal element selected from 1 to 30 mg / m ² of zirconium and titanium, and 1 to 100 mg / m ² by contact with a chemical conversion treatment solution having a pH of 2.0 to 6.0. and ² of the phosphorus element, and a oxygen element of 1 to 100 mg / m ^2, no coloring by chemical treatment, or less, high corrosion resistance and The method of producing a composite material to form a conversion coating layer having a color property, and the resulting chemical conversion film layer, characterized in that washing with water.   The main metal element is used in the preparation of the chemical conversion treatment liquid in the form of a hydrated oxide thereof or a salt of fluoride, chloride, oxychloride, bromide, iodide, or fluorine-containing acid. 9. A method for producing a composite material according to 8.   In the preparation of the chemical conversion treatment liquid, the halogen element is hydrochloric acid, hydrofluoric acid, hydroiodic acid, hydrobromic acid, chloride, fluoride, bromide or iodide of the main metal element, or fluorine-containing acid. The method for producing a composite material according to claim 8, wherein the composite material is used in the form of a salt.   The manufacturing method of the composite material of any one of Claims 8-10 in which the said chemical conversion liquid further contains a trivalent chromium element as a 1st additional metal element.   The manufacturing method of the composite material of Claim 11 whose density | concentration of the trivalent chromium element in the said chemical conversion liquid is 1-5000 ppm.   The said trivalent chromium element is used for preparation of the said chemical conversion liquid in the form of the hydrated oxide, a fluoride, a chloride, a bromide, an iodide, or the salt of a fluorine-containing acid. A method for producing a composite material.   The manufacturing method of the composite material of any one of Claims 8-13 in which the said chemical conversion liquid contains the 2nd additional metal element which consists of at least 1 sort (s) of element chosen from tungsten, molybdenum, vanadium, and cerium. Method.   The manufacturing method of the composite material of Claim 14 whose density | concentration of the 2nd additional metal element in the said chemical conversion liquid is 1-5000 ppm.   In the preparation of the chemical conversion treatment liquid, the second additional metal element is used in the form of a hydrated oxide, fluoride, chloride, bromide, iodide, or a salt of a fluorine-containing acid. The manufacturing method of the composite material of description.   When the substrate is an aluminum material or an aluminum alloy material, the nickel-phosphorus alloy plating base material is applied to the substrate after the nickel-phosphorus alloy plating treatment and the water washing and before the chemical conversion treatment. The method according to any one of claims 8 to 16, further comprising contacting hot water having a temperature of 50 ° C or higher, or contacting hot water having a temperature of 50 ° C or higher with the composite material obtained by performing the chemical conversion treatment and water washing. 2. A method for producing a composite material according to item 1.