JP2000313998A - Denatured pitch fluoride containing composite plating liquid and formation of composite plating film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enhance the water repellence of a composite plating film by incor porating a metal salt and fluorinated pitch treated by a diamine compound into the film. SOLUTION: A composite plating liquid consists of an aqueous solution prepared by dissolving the metal salt therein and dispersing the fluorinated pitch therein. The metal salt is the material for forming a metallic base material layer of composite plating film, for which salts of Ni, Cu, Zn, Sn, etc., are used. The fluorinated pitch previously treated by the diamine compound, i.e., the fluorinated pitch formed by reacting the diamine compound with the fluorinated pitch is used. The diamine compound is preferably expressed by formula, where R is 1 to 3C alkyl group and (n) is an integer from 2 to 5. N,N-dimethyl-1 and 3-propanediamine are more particularly preferable among these. The composite plating film is formed by immersing a prescribed base material into such plating liquid and applying electrolytic plating to the base material.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a plating solution and a method for forming a plating film, and more particularly to a composite plating solution and a method for forming a composite plating film.

[0002]

2. Description of the Related Art As a film for imparting water repellency to a metal or resin substrate, a film made of a fluorine-based resin such as polytetrafluoroethylene is known. However, since the fluororesin hardly softens and flows, it is difficult to form a uniform coating on the inner surface of a fine metal tube or the surface of a member having a complicated uneven shape. Therefore, as a film capable of imparting uniform water repellency to the surface of a member having a complicated shape or the like, a composite plating film in which particles of a fluorine-based compound or particles treated with a fluorine-based compound are dispersed is used. Proposed.

For example, Japanese Patent Application Laid-Open No. Hei 7-26397 discloses a composite plating film in which fine pitch fluoride particles are dispersed and eutectoid in a metal base material layer. This composite plating film has high water repellency because it contains fine pitch fluoride particles exhibiting high water repellency in the metal base material layer, and can be formed by a conventional plating method, and thus has a complicated shape and the like. Can be evenly applied to the surface or the like of a member having.

When the above-mentioned composite plating film is formed, usually, a metal salt for forming a metal base material layer, fine particles of pitch fluoride and fine particles of pitch fluoride are uniformly dispersed in water. A composite plating solution containing a surfactant is prepared, and a substrate is immersed in the composite plating solution to apply a plating method. However, since the composite plating film formed by this composite plating solution contains a surfactant which may be a cause of inhibiting water repellency, the water repellency originally expected by using pitch fluoride fine particles can be sufficiently exhibited. Hard to say.

An object of the present invention is to increase the water repellency of a composite plating film containing pitch fluoride.

[0006]

The composite plating solution according to the present invention contains a metal salt and pitch fluoride treated with a diamine compound. Here, the diamine compound is
For example, it is represented by the following general formula (1). In the formula, R represents an alkyl group having 1 to 3 carbon atoms, and n represents 2
5 to 5 are shown.

[0007]

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The diamine compound represented by the general formula (1) is, for example, N, N-dimethyl-1,3-propanediamine.

The method of forming a composite plating film according to the present invention is a method for forming a composite plating film in which pitch fluoride is dispersed in a metal base material layer on a substrate. This method includes a step of preparing a composite plating solution containing a metal salt for forming a metal base material layer and pitch fluoride treated with a diamine compound, and immersing the base material in the composite plating solution, Applying a plating method to the material. This method further includes, for example, a step of heat-treating the composite plating film obtained by the plating method.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The composite plating solution of the present invention comprises an aqueous solution in which a metal salt is dissolved and pitch fluoride is dispersed. Here, the metal salt is a material for forming a metal base material layer of the composite plating film, for example, noble metals such as nickel, copper, zinc, tin, iron, lead, cadmium, chromium, gold and silver, And salts such as alloys thereof.
Examples of such metal salts include chloride salts such as nickel chloride, carbonate salts such as nickel carbonate, and sulfamate salts such as nickel sulfamate.

On the other hand, fluorinated pitch is a known substance which can be produced by fluorinating pitch using fluorine gas, and is disclosed, for example, in Japanese Patent Application Laid-Open No. 62-275190.

The pitch used for producing such a fluorinated pitch generally has a layer structure in which aromatic condensed six-membered ring planes are laminated while being crosslinked by an aliphatic hydrocarbon group such as methylene. Usually, petroleum distillation residue,
Naphtha pyrolysis residue, ethylene bottom oil, coal liquefied oil and petroleum or coal heavy oil such as coal tar are distilled to remove low boiling components having a boiling point of less than 200 ° C.,
These are those synthesized by condensation of naphthalene or the like, and those further subjected to heat treatment or hydrogenation treatment. Specifically, isotropic pitch, mesophase pitch, hydrogenated mesophase pitch, mesocarbon microbeads composed of mesophase spheres formed after distilling petroleum-based or coal-based heavy oil to remove low-boiling components, etc. Can be mentioned.

When producing the desired fluorinated pitch using the above-mentioned pitch, the pitch is directly reacted with fluorine gas. The temperature at the time of this reaction is preferably set to about 0 to 350 ° C., and more preferably to the softening point of the pitch or lower. In addition, the fluorine gas pressure during the reaction is not particularly limited, but is generally preferably set to 0.07 to 1.5 atm. Note that, as the fluorine gas, a gas diluted with an inert gas such as nitrogen, helium, argon, or neon may be used.

Preferred fluorinated pitches usable in the present invention are substantially composed of carbon atoms and fluorine atoms, and the atomic ratio of fluorine to carbon (fluorine / carbon) is, for example, 0.5 to 1. It is about 8 powders. Such a fluorinated pitch exhibits the following characteristics (a), (b), (c) and (d).

(A) In powder X-ray diffraction, 2θ = 13
A peak with the maximum intensity is shown near ゜, and a peak with a smaller intensity than the maximum intensity peak is shown near 2θ = 40 °. (B) 290.0 ± 1.
The peak corresponding to CF at 0 eV and 292.5 ± 0.
A peak corresponding to CF ₂ is shown around 9 eV, and the ratio of the intensity of the peak corresponding to CF ₂ to the peak corresponding to CF is about 0.15 to 1.5. (C) A film can be formed by vacuum distillation. (D) The contact angle with water at 30 ° C. is 141 ± 8.
°.

In the present invention, pitch fluoride of a transparent resin can be used. The pitch of the fluorinated pitch in the form of a transparent resin is, for example, about 0.1 to 3 ° C./min, preferably 0.5 to 1.5 ° C. in a fluorine gas atmosphere.
The temperature is raised to about 250 to 400 ° C. at a rate of about 250 ° C./minute, and the temperature is raised for a predetermined time, for example, about 1 to 18 hours, preferably
It can be produced by reacting for about 12 hours. According to this method, for example, a fluorinated pitch in the form of a transparent resin having the following characteristics can be obtained.

F / C atomic ratio: 1.5 to 1.7 Light transmittance (250 to 900 nm): 90% Molecular weight: 1,500 to 2,000 Softening point: 150 to 250 ° C.

The fluorinated pitch used in the present invention has been previously treated with a diamine compound, that is, the fluorinated pitch has been reacted with a diamine compound, and has a surface activity by itself. Things.
The diamine compound used here is not particularly limited as long as it has two amino groups, and is a variety of known compounds. Preferably, the diamine compound is represented by the following general formula (1). .

[0019]

Embedded image

In the general formula (1), R represents an alkyl group having 1 to 3 carbon atoms, specifically, a methyl group, an ethyl group, an n-propyl group or an iso-propyl group. When the carbon number of the alkyl group represented by R exceeds 3, the steric hindrance may make it difficult for the diamine compound to react with the fluorinated pitch. On the other hand, n has shown the integer of 2-5. When n is 1, the diamine compound becomes unstable and handling may be difficult. Conversely, if it exceeds 5, it may be difficult to obtain a fluorinated pitch having a high surface activity.

Particularly preferred among the diamine compounds represented by the general formula (1) are those in which the alkyl group represented by R is a methyl group and n is 3,
1,3-propanediamine.

When reacting the above-mentioned pitch fluoride with the diamine compound, usually, a solution is prepared by dissolving both in a suitable solvent, and both solutions are mixed to react the pitch fluoride with the diamine compound. Let it. The solvent for dissolving the pitch fluoride and the diamine compound is not particularly limited as long as both can be dissolved, and for example, alcohols, furans, and the like can be used.

The reaction temperature at the time of reacting the pitch fluoride with the diamine compound is usually preferably set at room temperature to 100 ° C., more preferably at 10 to 40 ° C., and set at 10 to 20 ° C. More preferably, When the reaction temperature exceeds 100 ° C., the product may be tarred. In the above reaction, it is preferable to set the amount of the diamine compound to be substantially equivalent to the pitch fluoride. However, the amount of the diamine compound to be used is generally larger than that of the pitch fluoride. It is preferable to set

The composite plating solution of the present invention is prepared by preparing an aqueous solution in which the above-mentioned metal salt is dissolved in water, and in the aqueous solution, the above-mentioned fluorinated pitch treated with a diamine compound (hereinafter referred to as “the pitch”)
(Sometimes referred to as a modified fluorinated pitch) and then uniformly dispersed. The concentration of the metal salt in the aqueous solution prepared here is usually preferably set to 30 to 60% by weight. Metal salt concentration of 30% by weight
If it is less than 3, a metal base material layer having a required thickness may not be easily formed. On the other hand, if it exceeds 60% by weight, the viscosity of the composite plating solution becomes high, and it may be difficult to uniformly disperse the modified fluorinated pitch.

The content of the modified pitch fluoride in the composite plating solution of the present invention is preferably set so that the volume fraction of the modified pitch fluoride in the composite plating film is 10 to 60%. It is more preferable to set the amount to be about 40%, but usually it is 10 to 100 g /
1, preferably 30 to 70 g / l, can achieve such a volume fraction.

The composite plating solution of the present invention may contain various additives which can be usually added to the plating solution, such as a primary brightener, a secondary brightener, and a pigment for coloring the composite plating film, in addition to the above-mentioned various components. It may contain an agent.

As described above, the composite plating solution of the present invention can be produced by adding and mixing and dispersing the modified pitch fluoride and other additives in an aqueous solution in which the above-mentioned metal salt is dissolved. . Here, the modified fluorinated pitch is
As described above, pitch fluoride is treated with a diamine compound, and has surface activity by itself, so it is uniformly and stably dispersed in an aqueous solution without adding another surfactant to the aqueous solution. I can do it.

When a composite plating film is formed using the above-mentioned composite plating solution, a predetermined base material is immersed in the composite plating solution prepared as described above, and the plating method is applied to the base material. Apply.

At this time, it is preferable to sufficiently stir the composite plating solution so that the modified fluorinated pitch contained in the composite plating film is evenly and uniformly dispersed in the metal base material layer. The stirring method is not particularly limited, but various known methods such as screw stirring and stirring with a magnetic stirrer can be adopted.
In addition, as the plating method, a known electroless plating method or electrolytic plating method can be adopted. The plating conditions at this time can be set in the same manner as those employed in a general composite plating method. That is, the liquid temperature, the pH value, the current density, and the like can be appropriately set according to the properties of the base material and the type of the composite plating solution.

In such a method of forming a composite plating film, the metal salt contained in the composite plating solution is reduced to a metal, and the metal is electrodeposited on the substrate. Thereby, a metal base material layer is formed on the base material. At this time, the modified fluorinated pitch contained in the composite plating solution coeutects at the same time, and is uniformly dispersed in the metal base material layer. Thereby, a target composite plating film is formed on the base material.

The composite plating film thus formed is usually preferably further subjected to a heat treatment. By performing such a heat treatment, the water repellency of the composite plating film can be further increased. The heat treatment here is usually performed at a processing temperature of 150 to 300 ° C. and a processing time of 30 minutes to
Preferably, it is set to 2 hours. Heat treatment temperature is 150 ℃
If it is less than 1, it is necessary to set a long heat treatment time to obtain a sufficient heat treatment effect, which is not efficient. vice versa,
If the processing temperature exceeds 300 ° C., the composite plating film may be deteriorated.

The substrate on which the composite plating film is formed using the composite plating solution of the present invention usually needs to be imparted with water repellency by the composite plating film.

◎ A member requiring rust prevention. For example, various building materials and ship materials. ◎ Materials that may cause inconvenience if snow or icing occurs. For example, ice plates, transmission lines, parabolic antennas, etc. ◎ Materials that are required to have stain resistance, oil repellency, heat scorch, etc. For example, the inner surface of a dishwasher, the inner surface of a washing machine tank, a range hood, a ventilation fan, a table stove top plate, a table stove juice saucer, an oven plate, a grilled iron plate, a roster,
Genghis Khan hot pot, frying pan, goku, grill, gas stove, oven, microwave oven, rice cooker, barbecue stove, hot plate, pot, oven toaster, electric pot, electromagnetic induction heater, system kitchen top plate, sink, faucet, Mixing faucet, gas pipe inner and outer coats, etc. ◎ Materials requiring dew condensation prevention. For example, bathroom interior materials. ◎ Materials requiring water repellency and antifouling properties. For example, a bathtub. ◎ A member that is inconvenient if thermal conductivity is impaired. For example,
Exhaust top, heat exchanger fins, carbon fiber surface coat, carbon material coat, LNG vaporizer evaporator plate, copy roller, etc. ◎ Materials requiring mold release properties. For example, a mold. ◎ A member that requires water repellency and ice repellency. For example, parts for aircraft and helicopters. ◎ Materials that require slidability. For example, gas valve inner surface coating. ◎ A member that requires good liquid drainage. For example, liquid supply tubes such as micro syringe needles, pipettes, dispensers, separating funnels and general nozzles.

Specific materials constituting such a base material are not particularly limited as long as they can be applied with the electroplating method. Examples thereof include copper, stainless steel, general steel, aluminum and aluminum. Various metals such as alloys, and carbon materials such as carbon plates and graphite plates.

In the substrate, a portion where the composite plating film is to be formed may be roughened in advance into fine irregularities in order to enhance the adhesion with the composite plating film. As such a method of surface roughening, a method of chemically treating a substrate using an aqueous solution of an etching agent such as hydrofluoric acid, ammonium fluoride, or hydrochloric acid, or a shot blast treatment,
Mechanical processing methods such as sandblasting, liquid honing, and polishing using steel wire or steel wool can be employed.

Further, the substrate may be provided with a base plating layer such as a nickel plating layer or a copper plating layer on the surface on which the composite plating film is formed.

The composite plating film as described above can exhibit good water repellency due to the modified fluorinated pitch contained therein. Here, the modified fluorinated pitch in the composite plating solution is
Rather than being dispersed using a surfactant that inhibits the water repellency of the composite plating film, the composite plating film is dispersed by the surfactant activity of the composite plating film itself. Higher water repellency than when formed using a composite plating solution containing the same.

Further, since this composite plating film does not contain a surfactant, the occurrence of unevenness and discoloration are small, and the finished condition, that is, the appearance, is smaller than that obtained by using a composite plating solution containing a surfactant. Is good.

[0039]

EXAMPLES Production Example (Production of Modified Fluorinated Pitch) Pitch Fluoride (Prototype name “N-
6 ″) 100 g was dissolved in 200 ml of ethanol to obtain a pitch fluoride solution. 5 g of N, N-dimethyl-1,3-propanediamine was dissolved in 200 ml of ethanol to obtain a diamine compound solution. .

When the obtained pitch fluoride solution and the diamine compound solution were mixed at room temperature, the pitch fluoride and N, N-dimethyl-1,3-propanediamine reacted while generating heat, and a black-brown solid was formed. (Modified pitch fluoride)
was gotten.

Example 1 A nickel plating aqueous solution containing 360 g / l of nickel sulfamate, 45 g / l of nickel chloride and 30 g / l of boric acid was prepared. Then, the modified fluorinated pitch obtained in the production example was added at a rate of 50 g / l to sufficiently suspend the composite plating, and nickel carbonate was added as appropriate to adjust the composite plating to a pH of 4.2. A liquid was obtained.

The plate-like substrate was immersed in the obtained composite plating solution and subjected to an electrolytic plating treatment to form a composite plating film on the plate-like substrate. Here, a 5.0 cm × 5.0 cm stainless steel plate having a mirror surface (SUS
403), and the plating conditions were set as follows.

Current density: 3 A / dm ² Bath temperature: 50 ° C. Coating thickness: 10 μm

Example 2 The composite plating film obtained in Example 1 was heat-treated. The heat treatment conditions here were set at 300 ° C. for 30 minutes.

Comparative Example 1 In place of the modified pitch fluoride obtained in Production Example, the pitch fluoride used in Production Example was added to the nickel plating aqueous solution at a rate of 50 g / l, and this was added to the nickel plating aqueous solution. Example 1 and Example 1 except that the dispersion was carried out using a surfactant (cationic surfactant manufactured by Dainippon Ink Co., Ltd .: trade name “Megafax 150Br”) added at a ratio of 1.5 g / l. The same operation was performed to obtain a composite plating film.

Comparative Example 2 The composite plating film obtained in Comparative Example 1 was heat-treated. The heat treatment conditions here were set at 300 ° C. for 30 minutes.

Evaluation With respect to the composite plating films obtained in the respective Examples and Comparative Examples, the contact angle and the falling angle when distilled water was dropped were measured. The contact angle and the falling angle were determined for the composite plating film immediately after the formation (immediately after the formation) and for the case where the surface was strongly wiped 50 times using the product name “Kimwipe” of Jujo Kimberly Co., Ltd. (after the friction treatment). It was measured as follows. The finished condition (appearance) of the composite plating film was evaluated as follows. Table 1 shows the results.

(Contact angle) The contact angle was measured using a contact angle meter ("CA-A type" manufactured by Kyowa Interface Science Co., Ltd.).

(Tumble Angle) A water drop having a diameter of 3 mm was dropped on the contact angle meter used in the measurement of the contact angle, and the drop surface was gradually inclined from the horizontal plane, and the angle at which the water droplet flowed was defined as the fall angle.

(Finish Condition) The composite plating film was visually observed to determine the presence or absence of unevenness and discoloration. The evaluation criteria are as follows. ：: No unevenness or discoloration. Δ: There is slight unevenness and discoloration. X: There is clear unevenness and discoloration.

[0051]

[Table 1]

[0052]

The composite plating solution of the present invention can be prepared without using a surfactant since it contains a pitch fluoride having a surface activity which has been treated with a diamine compound. Therefore, the composite plating film formed by the composite plating solution exhibits high water repellency.

In the method for forming a composite plating film according to the present invention, since the composite plating solution of the present invention is used, a composite plating film having high water repellency can be formed.

Claims (5)

[Claims] A composite plating solution comprising a metal salt and pitch fluoride treated with a diamine compound. 2. The method according to claim 1, wherein the diamine compound is represented by the following general formula (1):
The composite plating solution according to claim 1, which is represented by: Embedded image (Wherein, R represents an alkyl group having 1 to 3 carbon atoms, and n represents 2 to
An integer of 5 is shown. ) 3. The method according to claim 1, wherein the diamine compound is N, N-dimethyl-
The composite plating solution according to claim 2, which is 1,3-propanediamine. 4. A method for forming, on a substrate, a composite plating film in which pitch fluoride is dispersed in a metal base material layer, comprising: a metal salt for forming the metal base material layer; A step of preparing a composite plating solution containing pitch fluoride treated with a diamine compound; and a step of immersing the substrate in the composite plating solution and applying a plating method to the substrate. A method for forming a composite plating film. 5. The method for forming a composite plating film according to claim 4, further comprising a step of heat-treating the composite plating film obtained by said plating method.