JP3521240B2 - Colored composite plating solution, colored composite plating method, and colored composite plating film - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD 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 Prior Art Generally, fluorinated resins such as fluorinated graphite and polytetrafluoroethylene (PTFE) are excellent in self-lubricating property, low friction property, water repellency and non-adhesive property. By depositing fine particles of a fluorinated resin together with a metal, a composite plating film having both the unique properties of a non-metal fluorinated resin and the properties of a metal serving as a matrix is formed.

The present inventors have found that when fluorinated pitch fine particles are used in place of the fluorinated resin as described above, a composite plating film having more improved water repellency can be obtained (Japanese Patent Laid-Open No. Hei 10 (1999) -242242). No. 4-329897).

However, although the composite plating film obtained by this method is extremely excellent in water repellency and the like, it is difficult to be colored, so that it can be used in a practical field where an aesthetic effect is required. It is restricted. That is, since the color of the matrix metal is dominant in the composite plating film containing fluorinated pitch fine particles as the eutectoid component, colorization in recent living environments (for example, housing materials, home appliances, glass appliances) It is not possible to fully meet the demand for colorization).

Color coating methods using paints, sealing materials and the like have been developed for colorizing metal products. However, such a color coating film has problems such as low strength, easy scratching, and low electrothermal property.

Furthermore, attempts have been made to obtain colored plating by adding colorants such as pigments and dyes to the plating solution and causing the colorants to eutectoid in the plating film. However, in order to clearly color the plating film, a large amount (50% or more of the plating layer weight) of colorant must be codeposited. In this case, it is unavoidable that the characteristics of the plating film are significantly deteriorated.

It is also considered that a colorant is co-deposited with a fluorinated resin to form a colored composite plating. However, in this case as well, the content of the co-deposition component in the metal matrix increases, so that the plating process is performed. The film properties cannot be maintained.

[0008]

SUMMARY OF THE INVENTION Therefore, the present invention aims to provide a new technique capable of coloring the composite plating film in which fluorinated pitch fine particles are co-deposited while maintaining the excellent performance. The main purpose is.

[0009]

The inventors of the present invention have made earnest studies in view of the above-mentioned state of the art, and as a result, colored fluoride pitch particles (hereinafter simply referred to as colored fluoride) as a co-deposition component during metal plating. It has been found that a colored composite plating film having a desired color can be obtained without impairing the excellent effect of the fluorinated pitch itself.

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 cationic fluoride at a pH of the plating solution and a colored fluorinated pitch.

2. Surfactant showing cationicity at pH of plating solution, colored fluorinated pitch and at least 1
Colored composite plating solution containing one kind of fluorinated resin.

3. A composite plating film obtained by co-depositing a colored fluoride pitch on a substrate by an electroplating method using a colored composite plating solution containing a cationic fluoride at a pH of the plating solution and a colored fluoride pitch. A colored composite plating method, which comprises forming.

4. Surfactant showing cationicity at pH of plating solution, colored fluorinated pitch and at least 1
A colored composite plating solution containing one kind of fluorinated resin is used to form a composite plating film obtained by co-depositing 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 obtained by co-depositing colored fluoride pitch in a metal plating film.

6. A colored composite plating film obtained by co-depositing a colored fluorinated pitch and at least one fluorinated resin in a metal plating film.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The colored fluorinated pitch used in the present invention is produced by the method described in, for example, Japanese Patent Application Nos. 7-278855 and 8-77698. You can

I. Basically, a method for producing a colored fluorinated pitch according to Japanese Patent Application No. 7-278855, "This method basically comprises: reacting a fluorinated pitch with a dye or a pigment using a reaction solvent, and then removing the solvent from the reaction solution. Coloring characterized by removing to obtain a crude colored fluorinated pitch, and then extracting and recovering the fluorinated pitch to which a dye or pigment is added using a fluorine-based solvent from the obtained crude fluorinated pitch It is a method for producing a fluorinated pitch ". The details are as follows.

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

The pitch used as a raw material for producing a fluorinated pitch usually has a structure in which fused aromatic six-membered ring planes are laminated, and the aromatic constituting the six-membered ring plane is an aliphatic hydrocarbon group such as methylene. It has a cross-linked structure. As the pitch for the production raw material of fluorinated pitch, petroleum distillation residue, naphtha thermal decomposition residue, ethylene bottom oil, coal liquefied oil, coal tar, etc. A pitch obtained by removing the low boiling point component, a pitch obtained by subjecting this pitch to a heat treatment and / or a hydrogenation treatment, and the like can be used. More specifically, as a pitch for a raw material for producing fluorinated pitch, for example, isotropic pitch, mesophase pitch, hydrogenated mesophase pitch, petroleum-based or coal-based heavy oil is distilled to remove low boiling point components. It is possible to use mesocarbon microbeads or the like composed of mesophase spheres formed after the above.

The fluorinated pitch can be obtained, for example, by reacting the above-mentioned raw material pitch with fluorine at about 0 to 350 ° C. More specifically, the raw material pitch and the fluorine gas are
The fluorinated pitch can be produced by bringing them into direct contact with each other at a temperature of about 0 to 350 ° C to cause a direct reaction. The preferred temperature for reacting the pitch with the fluorine gas is a temperature equal to or lower than the softening point of the pitch. The gas pressure of fluorine during the reaction is not particularly limited, but it is generally preferable to set it within the range of 0.07 to 1.5 atm. In this reaction, the fluorine gas may be used alone or may be diluted with an inert gas such as nitrogen, helium, argon or neon before use.

The fluorinated pitch produced by the above method is represented by the composition formula CFx (0.5 <x <1.8) and has 1-3 carbon atoms strongly bonded to each carbon atom by covalent bonds. Such a fluorinated pitch has the following (a),
The characteristics of (b), (c), (d) and (e) are shown.

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

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

(C) The film can be formed by vacuum vapor deposition.

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

(E) It is a white to yellowish white or brown solid, and is a very stable compound having excellent water resistance and chemical resistance.

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

F / C: 1.5 to 1.7 Light transmittance (250 to 900 nm): 90% Molecular weight: 1500-2000 Softening point: 150-250 ° 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 fluorinated pitch, it is preferable to use a dye or pigment having a functional group. Examples of the dye or pigment having a functional group include basic dyes and dispersible dyes. Preferable examples of dyes or pigments include methylene blue (tetramethylthionine chloride), chrysoidine (2,4-diaminoazobenzene), bismark brown (benzene-m-diazo-bis-m-phenylenediamine hydrochloride), etc. Is mentioned.

The preferable amount of the dye or pigment used varies depending on the type of the dye or pigment, the degree of coloring required, the purpose of use of the colored fluorinated pitch, etc., but generally it is 0 per 100 parts by weight of the fluorinated pitch. 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 the dye or pigment is used.

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

The fluorinated solvent can dissolve the fluorinated pitch appropriately and has a function of promoting the reaction between the fluorinated pitch and the dye or pigment. As the fluorine-based reaction solvent,
It is preferable to use a fluorinated solvent that can appropriately dissolve the fluorinated pitch as a raw material. 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 accelerate the reaction between the fluorinated pitch and the dye or pigment. As the 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 or tetrahydrofuran (THF).

In an embodiment in which a water-soluble organic solvent is used as the reaction solvent, in general, fluorinated pitch is insoluble in the water-soluble organic solvent, and therefore a dye or pigment is used instead of fluorinated pitch in water or a water-soluble organic solvent. It is necessary to better disperse with the solvent. Considering this point, the mixing ratio of the water-soluble organic solvent and water is 0 to 10 parts by weight, preferably 0.1 to 5 parts by weight, relative to 1 part by weight of the water-soluble organic solvent. . When the mixing ratio of water decreases, the dispersed state of the dye or pigment in the reaction liquid tends to deteriorate. On the contrary, when the mixing ratio of water increases, there is a drawback that the dispersed state of the fluorinated pitch, which is a water-repellent substance, in the reaction liquid becomes poor.

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

The reaction temperature between the fluorinated pitch 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. When the reaction is carried out at a low temperature, the reaction rate becomes slow, so it is preferable to carry out the reaction near the reflux temperature.

The method of removing the reaction solvent from the reaction solution is not particularly limited. For example, the reaction solvent may be distilled off to recover the crude colored fluorinated pitch.

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. Separation, purification and recovery of fluorinated pitch (colored fluorinated pitch) (1) Use of an extraction solvent that does not dissolve unreacted dye or pigment and can dissolve colored fluorinated pitch Extract the colored fluorinated pitch 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, relative to 1 part by weight of the coarse colored fluorinated pitch.

The extraction temperature is not particularly limited, and the colored fluorinated pitch can be extracted in the range of room temperature to the reflux temperature of the extraction solvent. Since the extraction speed becomes slower when the temperature is low, it is preferable to extract the colored fluorinated pitch near the reflux temperature. Further, it is preferable to recover the colored fluorinated pitch by evaporating the extraction solvent (fluorine-based solvent) from the extracted liquid containing the extracted colored fluorinated pitch.

(2) The unreacted dye or pigment is removed by washing the crude colored fluorinated pitch with a solvent which dissolves the unreacted dye or pigment and cannot dissolve the colored fluorinated pitch. And collect the colored fluoride 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. Roughly colored fluorinated pitch is dispersed in the washing solvent and thoroughly stirred,
For example, it is preferable to collect the colored fluoride pitch as a solid content by removing the washing solvent by filtration.

(3) The preferred amount of the dye or pigment added to the colored fluorinated pitch varies depending on the type of the dye or pigment, the degree of coloring required, the purpose of use, etc. It is useful to add 1 to 15% by weight, preferably 1 to 10% by weight of a dye or pigment.

II. Basically, a method for producing a colored fluorinated pitch according to Japanese Patent Application No. 8-77698 is basically carried out by "100 parts by weight of fluorinated pitch and 0.01 to 5 parts by weight of an inorganic pigment are dissolved in water in the presence of an ammonium salt. Of the heat-resistant colored fluorinated pitch, characterized in that the fluorinated pitch is reacted with an inorganic pigment to remove the solvent. The details are as follows.

Fluorinated pitch The same as above is used.

Inorganic Pigment Since the inorganic pigment is reacted with fluorinated pitch in the presence of an ammonium salt, an inorganic pigment having a functional group reactive with an ammonium group is preferable. Also, fluorinated pitch (generally
It is more preferable that the heat resistance is superior to that used at temperatures up to about 300 ° C).

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

The amount of the inorganic pigment used varies depending on the type, the required degree of coloring, the purpose of use of the colored fluorinated pitch, and the like.
It is about 1 to 5 parts by weight. When the amount of the inorganic pigment used is too small, the coloring is not sufficiently performed, whereas when the amount used is too large, the characteristics of the fluorinated pitch (such as water repellency) may deteriorate.

Ammonium Salt In the reaction between the fluorinated pitch and the inorganic pigment, it is essential that an ammonium salt be present. Examples of ammonium salts include ammonium sulfates (meaning ammonium sulfate and ammonium hydrogensulfate; the following "classes" mean the same thing), ammonium chloride, ammonium phosphates, ammonium nitrates, ammonium carbonates, and fluorine salts. Examples include ammonium chloride, 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. It

The amount of ammonium salt used is generally 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 carried out, whereas when the amount of the ammonium salt is too large, the viscosity of the reaction solution becomes high, 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 to be 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 others such as acetonitrile and tetrahydrofuran. Is exemplified.

The amount of the water-soluble organic solvent used is about 1 to 50 parts by weight, more preferably about 3 to 20 parts by weight, relative to 1 part by weight of the fluorinated pitch. When the organic solvent is used as an aqueous solution, it is used in an amount of 10 parts by weight or less, more preferably 0.1 to 5 parts by weight, relative to 1 part by weight of the organic solvent. When the amount of the organic solvent used is too small, the inorganic pigment is not uniformly dispersed, while when the amount is too large, the concentration of the inorganic pigment becomes too low, and in any case, the inorganic pigment and the fluorinated pitch. Does not react well. Also,
When the amount of water used is excessive, the amount of organic solvent decreases relatively, 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, the inorganic pigment and the ammonium salt are sufficiently dispersed and dissolved in the water-soluble organic solvent, and then the fluorinated pitch is dissolved. Add. The reaction temperature is not particularly limited, but at room temperature,
Alternatively, the reaction is carried out at a temperature not higher than the boiling point of the water-soluble organic solvent in a reaction vessel equipped with a reflux condenser. When the coloring is carried out quickly, it is preferable to carry out the reaction under heating. The fluorinated pitch after coloring is recovered by a conventional method, for example, by filtration.

The particle size of the colored fluorinated pitch obtained in the above-mentioned manner and used in the present invention is not particularly limited, but when it is larger than the thickness of the colored composite plating film, it is removed from the plated surface by friction. Since 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 depends on the material of the substrate material,
The thickness is usually about 1 to 50 μm, although it varies depending on the use and shape, the type of matrix metal and the like. Therefore, 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 the dispersion of fluorinated pitch in the composite plating solution and the composite plating film, it is desirable not to contain 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 eutectoid amount, etc.
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 characteristics (particularly water repellency) of the composite plating film, the colored fluorinated pitch and the fluorinated resin can be used in combination. As the fluorinated resin, polytetrafluoroethylene (hereinafter referred to as "PTFE"), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (hereinafter referred to as "PFA"), tetrafluoroethylene-hexafluoropropylene copolymer (hereinafter referred to as ""FEP") and the like. The fluorinated resin also does not contain coarse particles and usually has an average of 10
It is preferably about μm, and more preferably 1 μm or less on average. The addition amount of the fluorinated resin used in combination is not particularly limited, but the stirring state of the plating solution, the desired degree of coloring of the composite plating film, the co-deposition amount of the colored fluorinated pitch and the fluorinated resin, etc. are considered. The total amount of the colored fluorinated pitch and the fluorinated resin is about 200 g / l or less, preferably about 1 to 80 g / l.

When the colored fluorinated pitch and the fluorinated resin are used in combination, the ratio of the two may be determined so that the desired degree of coloring of the composite plating film can be obtained. The mixing 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 plated metal, etc. It is preferably 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 substrate such as a metal as a cathode can be adopted. As the plating solution to be used, any plating solution having various known compositions can be used. More specifically, for example, the colored fluorinated pitch (or the colored fluorinated pitch and the fluorinated fluorination is applied according to the plating method disclosed in JP-A-49-27443, JP-A-4-329897, etc.). Resin) in an aqueous solution of a plating metal salt, and co-deposited a colored fluoride pitch (or a colored fluoride pitch and a fluorinated resin) together with a matrix metal on a base material to obtain a non-metal fluoride. It suffices to form a composite plating film having both the unique properties of pitch (or fluorinated pitch and fluorinated resin) and the properties of the metal matrix.

Used in salt form in the electroplating bath,
As the matrix metal in the composite plating film,
For example, copper, nickel, chromium, zinc, cadmium, tin, iron, lead, noble metals and alloys thereof can be used. Electrolytic plating solutions containing these metals are known to have various compositions, 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 larger the volume fraction of the eutectoid, the lower the adhesion between the plating layer and the substrate. Also in the present invention, considering the adhesion between the plating film and the substrate, the volume fraction of the eutectoid (colored fluorinated pitch or colored fluorinated pitch and fluorinated resin) in the composite plated film is 60%. 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 the colored fluorinated pitch (or the colored fluorinated pitch and the fluorinated resin) in the composite plating film is usually about 15 to 50%, more preferably about 20 to 35%. .

A surfactant is used to uniformly disperse the colored fluorinated pitch (or the colored fluorinated pitch and the fluorinated resin) in the plating solution. As the surfactant, it is necessary to use one that exhibits a cationic property at the pH of the plating solution.For example, a water-soluble cationic system, a nonionic system, and an amphoteric interface that exhibits a cationic property at the pH of the plating solution. Activators can be used. Cationic surfactants include quaternary ammonium salts, secondary amines, tertiary amines, imidazolines, and the like, and nonionic surfactants include polyoxyethylene-based and polyoxyimine-based surfactants. Ester type etc. are mentioned. Among these, it is particularly preferable to use a fluorochemical surfactant having a CF bond in the molecule. Nonionic fluorine-based surfactants having a CF bond in the molecule show a cationic property only in the case of 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 colored fluorinated pitch (or colored fluorinated pitch and 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 very small. As a result, the amount of the surfactant adhering 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 brightening agent, a secondary brightening agent and a pigment for adjusting the color of the plating film may be added to the above composite plating solution.

In the present invention, as the base material, metals such as copper, stainless steel, general steel, aluminum and aluminum alloys, resins such as PTFE, 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 such as screw stirring and magnetic stirrer are used.
A method such as stirring by can be adopted.

The plating conditions depend on the material of the base material, the type of the composite plating solution used, and the like, and the same range of liquid temperature and pH as that generally adopted in the normal composite plating method.
It may be selected from a value, a current density and the like.

The colored composite plating film in the present invention does not necessarily have to be formed directly on the base material, but a known undercoating layer may be formed on a substrate material made of a metal such as copper or aluminum, a resin or a carbon material. After forming (for example, nickel plating, copper plating, etc.), a colored composite plating film may be formed.

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

[0067]

The colored composite plating film according to the present invention has both the unique properties of the non-metal colored fluoride pitch (or the colored fluoride pitch and the fluorinated resin) and the unique properties of the matrix metal. More specifically, this colored composite plating film is not only rich in color, but also has a high degree of lubricity and wear resistance derived from fluorinated pitch (or fluorinated pitch and fluorinated resin). Furthermore, 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 added to the plating solution should be significantly reduced. And even 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 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 the mixture was heated at 430 ° C. for 90 minutes. Then, the hydrogenated anthracene oil was removed at 300 ° C. under reduced pressure to obtain reduced pitch.

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

50 g of the obtained mesophase pitch was crushed, charged into a nickel reaction vessel, the system was evacuated,
After being filled 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 to obtain 158 g of fluorinated pitch particles. As a result of elemental analysis, its composition formula was CF _1.42 , and its average particle size was 10 μm.
It was m.

30 g of 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 3 times the amount of methanol at 60 ° C. to obtain 29.8 g of blue colored fluorinated pitch.

Example 1 The finely pulverized particles of blue fluorinated pitch (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. In addition, as a surfactant, a tertiary perfluoroammonium salt {trademark "Megafuck F-150", manufactured by Dainippon Ink and Chemicals, Inc., (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 Electrolyte 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 the positive electrode and the negative electrode, respectively, and the liquid temperature was 48 ± 5.
Under the conditions of ℃, pH 4.2, and current density of 1-5 A / dm ² , electrolytic plating is performed with a quantity of electricity of 1000 coulomb while stirring the screw to form a blue nickel-fluoride pitch composite plating film. The water repellency (contact angle of water immediately after plating and after vacuum drying) was examined. The results are shown in Table 1.

Example 2 Yellow inorganic dye (Chrysolidine: manufactured by Daiwa Kako Co., Ltd.)
A yellow fluorinated pitch was obtained by the same method as in Reference Example 1 except that was used, and then a nickel-fluoride pitch composite plating film was formed in the same manner as in Example 1. The water repellency of the obtained yellow composite plating film is shown in Table 1.

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 Dainichiseika Kogyo Co., Ltd.) was used. A nickel-fluoride pitch composite plating film was formed in the same manner as in 1. The water repellency of the obtained green composite plating film is shown in Table 1.

Example 4 The colored fluorinated pitch obtained in Reference Example 1 was used at 6.25 g /
1 and PTFE at a ratio of 50 g / l in the plating solution, and the same surfactant as in Example 1 was added to the colored fluorinated pitch and PTFE.
The plating operation was performed in the same manner as in Example 1 except that 30 mg was added to 1 g in 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 with respect to the total of 1 g of the colored fluorinated pitch and FEP.

Obtained 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 the colored fluorinated pitch was not used. Table 1 shows the water repellency of the obtained nickel plating film.

Comparative Example 2 A nickel-PTFE composite plating film was formed by plating 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 surfactant was added to 1 g of PTFE. Formed. The water repellency of the obtained composite plating film is shown in Table 1.

Comparative Example 3 A plating operation was performed in the same manner as in Example 1 except that the non-colored fluorinated pitch was used. The water repellency of the obtained composite plating film is shown in Table 1.

[0085]

[Table 1]

From the results shown in Table 1, it is apparent 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 immediately after the plating treatment.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Toshiyuki Maeda 4-1-2, Hirano-cho, Chuo-ku, Osaka-shi, Osaka Within Osaka Gas Co., Ltd. (56) Reference JP-A-4-329897 (JP, A) Kaihei 5-247353 (JP, A) JP 7-23862 (JP, A) JP 62-275190 (JP, A) JP 63-47396 (JP, A) JP 63-53297 ( JP, A) JP 52-6252 (JP, B2) JP 56-10398 (JP, B2) JP 3215627 (JP, B2) JP 3306606 (JP, B2) (58) Fields investigated (Int.Cl) . ⁷ , DB name) C25D 15/02

Claims (6)

(57) [Claims] 1. A colored composite plating solution containing a surfactant showing a cationic property at the pH of the plating solution and a colored fluorinated pitch. 2. A colored composite plating solution containing a surfactant having a cationic property at the pH of the plating solution, a colored fluorinated pitch and at least one fluorinated resin. 3. A colored composite plating solution containing a surfactant showing a cationic property at the pH of the plating solution and a colored fluorinated pitch is used to co-deposit the colored fluorinated pitch on a substrate by an electroplating method. Forming a composite plating film of 4. A substrate is colored by an electroplating method using a colored composite plating solution containing a surfactant having a cationic property at the pH of the plating solution, a colored fluorinated pitch and at least one fluorinated resin. A colored composite plating method, which comprises forming a composite plating film obtained by co-depositing fluorinated pitch and at least one kind of fluorinated resin. 5. A colored composite plating film obtained by co-depositing colored fluorinated pitch in a metal plating film. 6. A colored composite plating film obtained by co-depositing a colored fluorinated pitch and at least one fluorinated resin in a metal plating film.