JPH108296A - Colored composite plating liquid, colored composite plating method and colored composite plating film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel technique which enables the coloration of a composite plating film codepoosited with pitch fluoride particulates while maintaining the excellent performance thereof. SOLUTION: The colored composite plating liquid contains a surfactant exhibiting a cationic property at the pH of the plating liquid and colored pitch fluoride. The liquid contains the surfactant exhibiting the cationic property at the pH of the plating liquid, the colored pitch fluoride and at least one kind of fluororesin. The colored composite plating method forms the colored composite plating film codeposited with the colored pitch fluoride on a base material by an electroplating method by using the colored composite plating liquid contg. the surfactant exhibiting a cationic property at the pH of the plating liquid and the colored pitch fluoride.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a colored composite plating solution, a colored composite plating method, and a colored composite plating film.

[0002]

2. Description of the Related Art In general, fluorinated resins such as fluorinated graphite and polytetrafluoroethylene (PTFE) are excellent in self-lubricating properties, low friction properties, water repellency, non-adhesiveness and the like. By depositing fine particles of a fluorinated resin together with a metal, a composite plating film having both the inherent properties of a non-metallic fluorinated resin and the properties of a metal serving as a matrix has been formed.

The present inventors have found that a composite plating film having improved water repellency can be obtained when fine pitch fluoride particles are used in place of the above-mentioned fluorinated resin (Japanese Unexamined Patent Publication (Kokai) No. Heisei (Kokai) No. Hei 10-26139. 4-329,897).

[0004] However, the composite plating film obtained by this method is difficult to be colored even though it is extremely excellent in water repellency and the like, so that it can be used in a practical field where an aesthetic effect is required. Limited. That is, since the color of the metal serving as the matrix is dominant in the composite plating film containing fine pitch fluoride particles as the eutectoid component, colorization in recent living environments (for example, housing materials, home appliances, glassware) Such as colorization).

[0005] In order to color metal products, a color coating method using a paint, a sealing material or the like has been developed. However, such a color coating film has problems such as low strength, susceptibility to damage, and a decrease in electrothermal property.

Further, attempts have been made to obtain a colored plating by adding a coloring agent such as a pigment or a dye to a plating solution and eutecting the coloring agent into a plating film. However, in order to sharply color the plating film, a large amount (50% or more of the weight of the plating layer) of the colorant must be co-deposited. In this case, it is inevitable that the characteristics of the plating film are significantly reduced.

[0007] It has been considered to form a colored composite plating by co-depositing a coloring agent together with a fluorinated resin, but also in this case, since the content of the eutectoid component in the metal matrix increases, the Film properties cannot be maintained.

[0008]

Accordingly, an object of the present invention is to provide a new technique which enables the coloring of a composite plating film obtained by codepositing pitch fluoride fine particles while maintaining excellent performance. Main purpose.

[0009]

Means for Solving the Problems In view of the above-mentioned state of the art, the present inventors have conducted intensive studies and as a result, as a eutectoid component in metal plating, colored fluoride pitch particles (hereinafter simply referred to as colored fluorine). It has been found that a colored composite plating film having a desired color can be obtained without impairing the excellent effect of the pitch fluoride itself when using the fluorinated pitch.

That is, the present invention provides the following colored composite plating solution, colored composite plating method and colored composite plating film; A colored composite plating solution containing a surfactant exhibiting cationicity at the pH of the plating solution and colored fluoride pitch.

2. A surfactant exhibiting cationicity at the pH of the plating solution, a colored fluorinated pitch, and at least one
A colored composite plating solution containing a kind of fluorinated resin.

3. Using a colored composite plating solution containing a surfactant exhibiting cationicity at the pH of the plating solution and a colored pitch fluoride, a composite plating film formed by eutecting the colored pitch fluoride onto the substrate by electroplating. A colored composite plating method characterized by being formed.

4. A surfactant exhibiting cationicity at the pH of the plating solution, a colored fluorinated pitch, and at least one
Using a colored composite plating solution containing a kind of fluorinated resin, forming a composite plating film formed by eutecting colored fluorinated pitch and at least one kind of fluorinated resin on a substrate by electroplating. Characterized composite plating method.

5. A colored composite plating film formed by eutecting colored fluoride pitch into a metal plating film.

6. A colored composite plating film obtained by eutecting a colored fluorinated pitch and at least one fluorinated resin into a metal plating film.

[0016]

DETAILED DESCRIPTION OF THE INVENTION The colored fluorinated pitch used in the present invention can be produced, for example, by the method described in Japanese Patent Application Nos. 7-278855 and 8-77698. Can be.

I. Japanese Patent Application No. 7-278855 describes a method for producing a colored pitch fluoride. This method is basically based on "a reaction between a pitch fluoride and a dye or a pigment using a reaction solvent, and then removing the solvent from the reaction solution. Removal to obtain a coarse colored fluorinated pitch, and then extracting and recovering the fluorinated pitch to which a dye or pigment has been added from the obtained coarse fluorinated pitch using a fluorine-based solvent, and recovering it. Production method of pitch fluoride ". The details are as follows.

Pitch fluoride The pitch fluoride used in the method for producing a colored fluoride pitch can be obtained by fluorinating the pitch using a fluorine gas. Such a method for producing pitch fluoride is disclosed, for example, in Japanese Patent Application Laid-Open No. 62-275190.

The pitch used as a raw material for producing the fluorinated pitch generally has a structure in which aromatic condensed six-membered ring planes are laminated, and the aromatic constituting the six-membered ring plane is an aliphatic hydrocarbon group such as methylene. Has a crosslinked structure. As the pitch for the production material of fluorinated pitch, petroleum distillation residue, naphtha pyrolysis residue, ethylene bottom oil, coal liquefied oil, distilling petroleum or coal heavy oil such as coal tar and boiling point below 200 ° C Pitches obtained by removing low boiling components, and pitches obtained by heat treatment and / or hydrogenation treatment of the pitches can be used. More specifically, as the pitch for the production raw material of the fluorinated pitch, for example, isotropic pitch, mesophase pitch, hydrogenated mesophase pitch, distilling petroleum or coal heavy oil to remove low boiling components For example, mesocarbon microbeads formed of mesophase spheres generated after the above can be used.

The fluorinated pitch can be obtained, for example, by reacting the above raw material pitch with fluorine at about 0 to 350 ° C. More specifically, the raw material pitch and fluorine gas are mixed.
Pitch fluoride can be produced by contacting and directly reacting at a temperature of about 0 to 350 ° C. A preferred temperature at which the pitch reacts with the fluorine gas is a temperature equal to or lower than the softening point of the pitch. The gas pressure of fluorine at the time of the reaction is not particularly limited, but is generally preferably in the range of 0.07 to 1.5 atm. In this reaction, fluorine gas may be used alone or may be diluted with an inert gas such as nitrogen, helium, argon, or neon.

The fluorinated pitch produced by the above method is represented by the composition formula CFx (0.5 <x <1.8), in which one to three fluorine atoms are firmly bonded to each carbon atom by a covalent bond. Such a fluorinated pitch is represented by the following (a):
The characteristics of (b), (c), (d) and (e) are shown.

(A) In powder X-ray diffraction, 2θ = 13
The peak of the maximum intensity is shown around °, and a peak smaller in intensity than the peak of the maximum intensity is shown near 2θ = 40 °.

(B) In X-ray photoelectron spectroscopy analysis, 29
A peak corresponding to a CF group is shown at 0.0 ± 1.0 eV,
Further, a peak corresponding to a CF ₂ group is shown around 292.5 ± 0.9 eV, and a CF corresponding to a peak corresponding to a CF group is shown.
The ratio of the peak intensities corresponding to the _two groups is 0.15 to 1.5.
It is about.

(C) A film can be formed by vacuum evaporation.

(D) The contact angle with water at 30 ° C. is 141 ° ± 8 °.

(E) White to yellow-white or brown solid, excellent in water resistance and chemical resistance, and a very stable compound.

As a raw material for producing the colored fluorinated pitch, a fluorinated pitch in the form of a transparent resin can be used. Pitch fluoride in the form of a transparent resin, for example, in a fluorine gas-containing atmosphere of pitch fluoride, 0.1 ~
The temperature is raised to about 250 to 400 ° C. at a rate of about 3 ° C./min, preferably about 0.5 to 1.5 ° C./min, for a predetermined time, for example, about 1 to 18 hours, preferably 6 to 112 hours.
It is obtained by reacting for about an hour. Such a transparent resinous fluoride pitch exhibits, for example, the following characteristics.

F / C: 1.5 to 1.7 Light transmittance (250 to 900 nm): 90% Molecular weight: 1500 to 2000 Softening point: 150 to 250 ° C.

Dyes and Pigments The dyes and pigments used in the production of the colored fluorinated pitch are not particularly limited, and various commonly used dyes and pigments can be used. From the viewpoint of reactivity with pitch fluoride, it is preferable to use a dye or pigment having a functional group. Examples of the dye or pigment having a functional group include a basic dye and a disperse dye. Specific examples of preferred dyes or pigments include methylene blue (tetramethylthionine chloride), chrysoidin (2,4-diaminoazobenzene), and bismark brown (benzene-m-diazo-bis-m-phenylenediamine hydrochloride). Is mentioned.

The preferred amount of the dye or pigment varies depending on the type of the dye or pigment, the required degree of coloring, the purpose of the colored fluorinated pitch, and the like. 0.1 to 20 parts by weight, preferably 1.0 to 15 parts by weight, more preferably about 3.0 to 10 parts by weight of a dye or pigment is used.

Reaction Solvent In the coloring reaction of the fluorinated pitch, 1 to 100 parts by weight, preferably 5 to 30 parts by weight, of the reaction solvent is used per 1 part by weight of the fluorinated pitch. As the reaction solvent, it is preferable to use a fluorinated solvent or an organic solvent or a mixed solvent of an organic solvent and water.

The fluorinated solvent can appropriately dissolve the pitch fluoride and has an action to promote the reaction between the pitch fluoride and the dye or pigment. As the fluorine-based reaction solvent,
It is preferable to use a fluorinated solvent capable of appropriately dissolving the raw material pitch fluoride. Examples of such a fluorine-based solvent include hexafluorobenzene, perfluorodecalin, perfluorodecahydrophenanthrene, trifluorobenzene, 1,1,2-trichloro, 1,2,2-trifluoroethane, and the like. Can be mentioned.

The organic solvent acts as a dispersion medium for the dye or pigment, and can promote the reaction between the pitch fluoride and the dye or pigment. As a reaction solvent, it is preferable to use a water-soluble organic solvent or a mixed solvent of a water-soluble organic solvent and water. Examples of the water-soluble organic solvent include alcohols such as methanol, ethanol, propanol and butanol, ketones such as acetone, ethyl methyl ketone, diethyl ketone and methyl isopropyl ketone, acetonitrile and tetrahydrofuran (THF).

In an embodiment in which a water-soluble organic solvent is used as a reaction solvent, since pitch fluoride is generally insoluble in a water-soluble organic solvent, a dye or pigment is replaced with water or a water-soluble organic solvent instead of pitch fluoride. It needs to be better dispersed in the solvent. In consideration of this point, the mixing ratio of the water-soluble organic solvent and water is preferably 0 to 10 parts by weight of water, preferably 0.1 to 5 parts by weight with respect to 1 part by weight of the water-soluble organic solvent. . When the mixing ratio of water decreases, the state of dispersion of the dye or pigment in the reaction liquid tends to deteriorate. Conversely, when the mixing ratio of water increases, there is a disadvantage that the dispersion state of pitch fluoride, which is a water-repellent substance, in the reaction solution is deteriorated.

Reaction Conditions In the production of the colored pitch fluoride, the pitch fluoride, the dye or pigment and the solvent are stirred to react the pitch fluoride with the dye or pigment, and the dye or pigment is added to the pitch fluoride. Let it.

The reaction temperature between the pitch fluoride and the dye or pigment is not particularly limited, and may be in the range of room temperature to the reflux temperature of the reaction solvent. If the reaction is carried out at a low temperature, the reaction rate becomes slow.

The method for removing the reaction solvent from the reaction solution is not particularly limited. For example, the reaction solvent can be distilled off by distillation, and coarse colored pitch fluoride can be recovered.

Recovery of Colored Fluorinated Pitch Next, unreacted dye or pigment was removed from the crude colored fluorinated pitch obtained as described above by the method exemplified below, and the dye or pigment was added. Separate, purify, and recover the pitch fluoride (colored pitch fluoride). (1) Use an extraction solvent that does not dissolve unreacted dyes or pigments and can dissolve the colored pitch fluoride. The colored fluorinated pitch is extracted from the activated pitch. As the extraction solvent, the above-mentioned fluorine-based solvent (which can be used as a reaction solvent) can be used. The amount of the fluorinated solvent used is 1 to 100 parts by weight, preferably 5 to 30 parts by weight, per 1 part by weight of the coarse colored fluorinated pitch.

There is no particular limitation on the extraction temperature, and the colored fluorinated pitch can be extracted in a range from room temperature to the reflux temperature of the extraction solvent. Since the extraction speed becomes slower if it is performed at a low temperature, it is preferable to perform the extraction of the colored fluorinated pitch near the reflux temperature. Further, it is preferable to recover the colored fluorinated pitch by evaporating the extraction solvent (fluorinated solvent) from the extracted extract containing the colored fluorinated pitch.

(2) The unreacted dye or pigment is removed by washing the coarse colored pitch using a solvent that dissolves unreacted dye or pigment and cannot dissolve the colored pitch. To collect the colored fluorinated pitch. As the washing solvent, the above-mentioned water-soluble organic solvent (which can be used as a reaction solvent) or a mixed solvent of a water-soluble organic solvent and water can be used. After the coarse colored fluorinated pitch is dispersed in the washing solvent and sufficiently stirred,
For example, it is preferable to collect the colored fluorinated pitch as a solid by removing the washing solvent by filtration.

(3) The preferred amount of the dye or pigment to be added to the colored fluorinated pitch varies depending on the type of the dye or pigment, the required degree of coloring, the purpose of use, and the like. A dye or pigment to which about 1 to 15% by weight, preferably about 1 to 10% by weight is added is useful.

II. Japanese Patent Application No. 8-77698 discloses a method of producing a colored pitch fluoride. A method for producing a heat-resistant colored fluorinated pitch, comprising dispersing in an organic solvent, reacting the fluorinated pitch with an inorganic pigment, and removing the solvent. The details are as follows.

Fluoride pitch The same as described above is used.

Inorganic Pigments Since inorganic pigments react with pitch fluoride in the presence of an ammonium salt, those having a functional group reactive with ammonium groups are preferred. Also, pitch fluoride (generally
It is more preferable that the heat resistance is superior to that at a temperature up to about 300 ° C.).

Examples of such inorganic pigments include single metal inorganic pigments such as chrome-based yellow, molybdenum-based orange, cadmium-based red, cadmium-based yellow, and cadmium-based orange: Ti-Ba-Ni-based (yellow) , Ti-
Sb-Cr (yellow), Zn-Fe (brown), Ti-Co-Ni
-Zn (green), Co-Al-Cr (green), Co-Al (blue), Co-Al-Cr (blue), Cu-Cr (brown), Cu-Fe-Mn ( Black).

The amount of the inorganic pigment to be used varies depending on its kind, the required degree of coloring, the purpose of the colored fluorinated pitch, and the like.
It is about 01 to 5 parts by weight. When the amount of the inorganic pigment used is too small, coloring is not sufficiently performed. On the other hand, when the amount used is too large, properties (such as water repellency) of pitch fluoride may be deteriorated.

In the reaction between the ammonium salt fluoride pitch and the inorganic pigment, it is essential that an ammonium salt is present. Examples of the ammonium salt include ammonium sulfates (ammonium sulfate and ammonium hydrogen sulfate; hereinafter, “type” means the same thing), ammonium chloride, ammonium phosphates, ammonium nitrates, ammonium carbonate, and fluorine. Examples thereof include ammonium fluoride, ammonium sulfite, ammonium acetate, ammonium lactate, ammonium formate, ammonium succinate, ammonium citrate, ammonium phthalate, ammonium adipate, ammonium benzoate, ammonium tartrate, ammonium diethylcarbamate, and ammonium oxalate. You.

The amount of the ammonium salt to be used is usually 0.1 to 100 parts by weight of fluorinated pitch as ammonium.
It is about 10 parts by weight. When the amount of the ammonium salt used is too small, the coloring reaction is not sufficiently performed. On the other hand, when the amount is too large, the viscosity of the reaction solution increases, which is not preferable.

Reaction Solvent In the coloring reaction of the fluorinated pitch, the reaction components are sufficiently dissolved or dispersed in a water-soluble organic solvent or an aqueous solution of a water-soluble organic solvent and reacted.

Examples of such water-soluble organic solvents include lower aliphatic alcohols such as methanol, ethanol, propanol and butanol; ketones such as acetone, methyl ethyl ketone, diethyl ketone and methyl isobutyl ketone; and acetonitrile and tetrahydrofuran. Is exemplified.

The amount of the water-soluble organic solvent to be used is about 1 to 50 parts by weight, more preferably about 3 to 20 parts by weight, based on 1 part by weight of the fluorinated pitch. When an organic solvent is used as an aqueous solution, water is used in an amount of 10 parts by weight or less, more preferably about 0.1 to 5 parts by weight, based on 1 part by weight of the organic solvent. If the amount of the organic solvent is too small, the inorganic pigment is not uniformly dispersed, whereas if it is too large, the concentration of the inorganic pigment is too low, and in any case, the inorganic pigment and the fluorinated pitch Does not work well. Also,
If the amount of water used is excessive, the amount of the organic solvent is relatively reduced, so that the inorganic pigment cannot be uniformly dispersed.

Reaction Conditions Since fluorinated pitch is not easily dispersed in a water-soluble organic solvent, first, an inorganic pigment and an ammonium salt are sufficiently dispersed and dissolved in a water-soluble organic solvent. Add. The reaction temperature is not particularly limited, but at room temperature,
Alternatively, the reaction is carried out at a temperature lower than the boiling point of the water-soluble organic solvent in a reaction vessel equipped with a reflux condenser. When coloring is performed promptly, the reaction is preferably performed under heating. The fluorinated pitch after coloring is collected by a conventional method, for example, by filtration.

For example, the particle size of the colored fluorinated pitch obtained in the above-described manner and used in the present invention is not particularly limited. Since the particles fall off, it is desirable to use fine particles smaller than the plating film.
The thickness of the composite plating film according to the present invention, the material of the substrate material,
Although it varies depending on the use and shape, the type of the matrix metal, and the like, it is usually about 1 to 50 μm. Accordingly, the particle size of the fluorinated pitch may be determined in consideration of the thickness of the composite plating film, but is usually about 10 μm on average, and more preferably 1 μm or less on average. Further, in order to ensure the uniformity of dispersion of the pitch fluoride in the composite plating solution and the composite plating film, it is desirable not to include coarse particles of 30 μm or more. The amount of the colored fluorinated pitch added to the composite plating solution is not particularly limited, but may be determined in consideration of the stirring state of the plating solution, the desired amount of eutectoid, and the like.
It is about 00 g / l or less, preferably about 1 to 80 g / l.

In the present invention, in order to further improve the properties (particularly, water repellency) of the composite plating film, a colored fluorinated pitch and a fluorinated resin can be used in combination. Examples of the fluorinated resin include polytetrafluoroethylene (hereinafter, referred to as “PTFE”), tetrafluoroethylene-perfluoroalkylvinyl ether copolymer (hereinafter, referred to as “PFA”), and tetrafluoroethylene-hexafluoropropylene copolymer (hereinafter, referred to as “PTFE”). FEP ”). The fluorinated resin also contains no coarse particles and usually has an average of 10
It is preferably about μm, more preferably 1 μm or less on average. The amount of the fluorinated resin to be used in combination is not particularly limited, either, but the stirring state of the plating solution, the desired degree of coloring of the composite plating film, the amount of eutectoid between the colored fluorinated pitch and the fluorinated resin, etc. are taken into consideration. The total of the colored fluorinated pitch and the fluorinated resin is also about 200 g / l or less, preferably about 1 to 80 g / l.

In the case where the colored pitch fluoride and the fluorinated resin are used in combination, the ratio between the two may be determined so that the desired degree of coloring of the composite plating film is obtained. The blending ratio of the two is not particularly limited because it varies depending on the color of the colored fluorinated pitch, the degree of coloring, the type of the plating metal, and the like. It is preferred to be about 10 parts by weight.

For forming the eutectoid colored composite plating in the present invention, a known electrolytic plating method capable of depositing a matrix metal on the surface of a base material such as a metal as a cathode can be employed. Regarding the plating solution to be used, any of various known plating solutions can be used. More specifically, for example, according to the plating method disclosed in JP-A-49-27443, JP-A-4-329897, etc., the colored fluorinated pitch (or Resin and an aqueous solution of a plating metal salt, and co-deposit the colored pitch fluoride (or the colored pitch fluoride and the fluorinated resin) together with the matrix metal on the substrate to obtain a non-metallic fluoride. What is necessary is just to form a composite plating film having both the inherent properties of the pitch (or the pitch fluoride and the fluorinated resin) and the properties of the matrix metal.

In the electroplating bath, it is used in the form of a salt,
As a matrix metal in the composite plating film,
For example, any of copper, nickel, chromium, zinc, cadmium, tin, iron, lead, precious metals, and alloys thereof can be used. Various types of electroplating solutions containing these metals are known, and in the present invention, any of these known plating solutions can be used.

In general, in a composite plating film composed of a metal and an eutectoid, the adhesion between the plating layer and the substrate decreases as the volume fraction of the eutectoid increases. Also in the present invention, the volume fraction of eutectoid (colored fluorinated pitch or colored fluorinated pitch and fluorinated resin) in the composite plating film is 60% in consideration of the adhesion between the plating film and the substrate. Is the limit. On the other hand, when the volume fraction of the colored fluorinated pitch (or the colored fluorinated pitch and the fluorinated resin) is too low, the coloring is not sufficient and the water repellency is not sufficiently improved. Therefore, in the present invention, the volume fraction of colored pitch fluoride (or colored pitch fluoride and fluorinated resin) in the composite plating film is usually about 15 to 50%, more preferably about 20 to 35%. .

To uniformly disperse the colored fluorinated pitch (or the colored fluorinated pitch and the fluorinated resin) in the plating solution, a surfactant is used. It is necessary to use a surfactant that exhibits cationicity at the pH of the plating solution, for example, a water-soluble cationic type, a nonionic type, and an amphoteric interface that exhibits cationicity at the pH of the plating solution. An activator can be used. Examples of the cationic surfactant include quaternary ammonium salts, secondary amines, tertiary amines, and imidazolines, and examples of the nonionic surfactant include polyoxyethylene, polyoxyimine, Ester type and the like can be mentioned. Among these, it is particularly preferable to use a fluorinated surfactant having a CF bond in the molecule. A nonionic fluorine-based surfactant having a CF bond in a molecule shows cationicity only in an acidic plating bath.

The amount of the surfactant added to the plating solution is preferably about 1 to 100 mg per 1 g of the colored fluorinated pitch (or the colored fluorinated pitch and the fluorinated resin).
More preferably, it is about 50 mg. The colored fluorinated pitch (or the colored fluorinated pitch and the fluorinated resin) used as the substance to be dispersed in the present invention is uniformly dispersed in the plating solution even when the amount of the surfactant used is extremely small. As a result, the amount of the surfactant attached to the colored fluorinated pitch (or the colored fluorinated pitch and the fluorinated resin) is reduced, so that high water repellency can be exhibited even immediately after the plating film is formed.

In the present invention, if necessary, known additives such as a primary brightener, a secondary brightener, and a pigment for adjusting the color of the plating film may be further added to the composite plating solution.

In the present invention, as the substrate, metals such as copper, stainless steel, general steel, aluminum and aluminum alloys, resins such as PTFE, and carbon materials such as carbon plates and graphite plates are used.

In forming the colored composite plating film by the method of the present invention, in order to uniformly disperse the colored fluorinated pitch (or the colored fluorinated pitch and the fluorinated resin),
It is preferable to perform the plating operation while stirring the composite plating solution. The stirring method is not particularly limited, and ordinary mechanical stirring means, for example, screw stirring, magnetic stirrer, etc.
And a method such as stirring by means of

The plating conditions are set to the same range of solution temperature and pH as those generally employed in the ordinary composite plating method, depending on the material of the base material, the type of the composite plating solution to be used, and the like.
What is necessary is just to select from a value, a current density, etc.

The colored composite plating film in the present invention does not necessarily need to be formed directly on a substrate, but may be formed on a substrate material made of a metal such as copper or aluminum, a resin, a carbon material, or the like. (For example, nickel plating, copper plating, etc.), a colored composite plating film may be formed.

The coating formed after the plating operation is washed with water and dried according to a conventional method. The method for drying the plating film is not particularly limited, and natural drying may be used, but vacuum drying is more preferable from the viewpoint of handling of the plated product. Vacuum drying conditions are not particularly limited, but usually 5
The reaction is carried out under reduced pressure of about 300 mmHg at ordinary temperature to about 120 ° C, more preferably at about 40 to 80 ° C.

[0067]

The colored composite plating film according to the present invention has both the intrinsic properties of the non-metallic colored pitch fluoride (or the colored pitch fluoride and the fluorinated resin) and the intrinsic properties of the matrix metal. More specifically, this colored composite plating film is not only rich in color but also has high lubricity and abrasion resistance derived from pitch fluoride (or pitch fluoride and fluorinated resin). In addition, it exhibits particularly excellent durability and water repellency.

Further, since the dispersibility of the colored fluorinated pitch (or the colored fluorinated pitch and the fluorinated resin) in the plating solution is very good, the amount of the surfactant to be added to the plating solution is significantly reduced. And immediately after plating,
Good water repellency is exhibited.

In particular, when the colored fluorinated pitch and the fluorinated resin are used in combination, the water repellency can be further improved without substantially impairing the effect of coloring the composite plating film.

[0070]

EXAMPLES Reference examples (production examples of fluorinated pitch fine particles), examples and comparative examples are shown below to further clarify the features of the present invention.

Reference Example 1 A double amount of hydrogenated anthracene oil was added to a coal tar pitch having a softening point of 100 ° C., a quinoline-insoluble content of 0.15% by weight, and a benzene-insoluble content of 30% by weight, and was heated at 430 ° C. for 90 minutes. Thereafter, the hydrogenated anthracene oil was removed at 300 ° C. under reduced pressure to obtain a reduced pitch.

Next, nitrogen gas was introduced into the obtained reduced pitch to remove low molecular weight components, followed by thermal polymerization at 400 ° C. for 5 hours, a softening point of 320 ° C., a quinoline-insoluble content of 73% by weight, and a benzene-insoluble content of 99% by weight. % And a mesophase pitch having a mesophase content of 93% by weight or more.

50 g of the obtained mesophase pitch was pulverized, charged into a nickel reaction vessel, and the system was evacuated to a vacuum.
After filling with argon gas, a mixed gas of 20% fluorine and 80% argon was passed at 70 ° C. at an average flow rate of 600 cc / min and reacted for 25 hours. As a result, 158 g of pitch fluoride particles were obtained. As a result of elemental analysis, the composition formula was CF _1.42 , and the average particle size was 10 μm.
m.

30 g of the fluorinated pitch obtained as described above
To this was added 0.3 g of a blue inorganic dye (Methylene Blue FZ: manufactured by Daiwa Kako Co., Ltd.), and the mixture was reacted in a three-fold amount of methanol at 60 ° C. to obtain 29.8 g of a blue-colored fluoride pitch.

Example 1 Finely pulverized blue fluoride pitch particles (average particle size: 1.3 μm) obtained in Reference Example 1 were added to a nickel electrolytic bath having the following composition at a rate of 50 g / l. The third Kyupa as surfactants - fluoro salt {trademark "Megafac F-0.99", Dainippon Ink Chemical Co., Ltd., (C ₈ F ₁₇ S
O ₂ NH (CH ₂ ) ₃ N ⁺ (CH ₃ ) ₃ .Cl ⁻ )} was added at a ratio of 25 mg to 1 g of the colored fluorinated pitch.

Nickel sulfamate electrolytic bath composition Nickel sulfamate 360 g / l Nickel chloride 45 g / l Boric acid 30 g / l Then, a nickel plate and a copper plate of 0.5 mm × 3 cm × 5 cm were used as a positive electrode and a negative electrode, respectively, and the liquid temperature was 48 ± 5.
° C., pH 4.2, at a current density of 1-5A / dm ^2, while stirring screw, and subjected to electrolytic plating with electric quantity of 1000 coulomb, blue nickel - to form a pitch fluoride composite plating film, the Water repellency (contact angle of water immediately after plating and after vacuum drying) was examined. Table 1 shows the results.

Example 2 Yellow inorganic dye (Chrysolidine: manufactured by Daiwa Kako Co., Ltd.)
After obtaining a yellow pitch fluoride by the same method as in Reference Example 1 except for using, a nickel-fluoride pitch composite plating film was formed in the same manner as in Example 1. Table 1 shows the water repellency of the obtained yellow composite plating film.

Example 3 A yellow fluorinated pitch was obtained in the same manner as in Reference Example 1 except that a green inorganic dye (Master Fine Color MF5320: manufactured by Dainichi Seika Kogyo Co., Ltd.) was used. In the same manner as in Example 1, a nickel-fluoride pitch composite plating film was formed. Table 1 shows the water repellency of the obtained green composite plating film.

Example 4 The colored fluorinated pitch obtained in Reference Example 1 was used in an amount of 6.25 g /
l, PTFE in the plating solution at a rate of 50 g / l, and the same surfactant as in Example 1 with colored fluoride pitch and PTFE
The plating operation was carried out in the same manner as in Example 1 except that 30 mg was added to 1 g of the total. Table 1 shows the water repellency of the obtained blue nickel-fluoride pitch-PTFE composite plating film.

Example 5 A plating operation was performed in the same manner as in Example 4 except that FEP was used instead of PTFE. However, the amount of the surfactant was 61 mg per 1 g of the total of the colored fluorinated pitch and FEP.

The resulting blue nickel-fluoride pitch-
Table 1 shows the water repellency of the FEP composite plating film.

Comparative Example 1 A nickel plating film was formed on a copper plate in the same manner as in Example 1 except that no colored fluoride pitch was used. Table 1 shows the water repellency of the obtained nickel plating film.

Comparative Example 2 Plating was carried out in the same manner as in Example 1 except that PTFE was used in place of the colored fluorinated pitch, and 4.5 mg of a surfactant was added to 1 g of PTFE to form a nickel-PTFE composite plating film. Formed. Table 1 shows the water repellency of the obtained composite plating film.

Comparative Example 3 A plating operation was carried out in the same manner as in Example 1 except that fluorinated pitch in an uncolored state was used. Table 1 shows the water repellency of the obtained composite plating film.

[0085]

[Table 1]

From the results shown in Table 1, it is clear that when the colored composite plating solution according to the present invention is used, a colored plating film having excellent water repellency can be obtained even immediately after plating.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Toshiyuki Maeda Osaka Gas Co., Ltd. 4-1-2, Hirano-cho, Chuo-ku, Osaka-shi, Osaka

Claims (6)

[Claims] 1. A colored composite plating solution containing a surfactant exhibiting cationicity at the pH of the plating solution and colored fluorinated pitch. 2. A colored composite plating solution comprising a surfactant exhibiting cationicity at the pH of the plating solution, a colored fluorinated pitch and at least one fluorinated resin. 3. Using a colored composite plating solution containing a surfactant exhibiting cationicity at the pH of the plating solution and a colored fluorinated pitch, the colored fluorinated pitch is co-deposited on the substrate by electroplating. A composite plating method characterized by forming a composite plating film. 4. A base material is colored by electroplating using a colored composite plating solution containing a surfactant exhibiting cationicity at the pH of the plating solution, a colored fluorinated pitch and at least one fluorinated resin. A colored composite plating method comprising forming a composite plating film obtained by eutecting pitch fluoride and at least one fluorinated resin. 5. A colored composite plating film obtained by codepositing colored fluoride pitch in a metal plating film. 6. A colored composite plating film obtained by eutecting colored fluorinated pitch and at least one fluorinated resin into a metal plating film.