JP3306606B2 - Substrate provided with highly durable and highly water-repellent composite plating film, method for producing the same, and ice plate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a substrate material provided with a highly durable and highly water-repellent composite plating film obtained by codepositing fine pitch fluoride particles having excellent water repellency, lubricity and ice repellency. The present invention relates to a production method and an ice making plate provided with such a highly durable and highly water repellent composite plating film.

[0002]

2. Description of the Related Art Generally, fluorine compounds such as fluorinated graphite and polytetrafluoroethylene (PTFE) have excellent self-lubricating properties, low friction properties, water repellency, non-adhesiveness and the like.
Such fine particles of a fluorine compound are precipitated together with a metal to form a composite plating film having both excellent intrinsic properties and properties of a metal.

The present inventors have found that a composite plating film having improved water repellency can be obtained when pitch fluoride is used in place of the above-mentioned fluorine compound (Japanese Patent Application Laid-Open No. HEI 4- Hei 4). No. 329897). However, even in the composite plating film obtained by this method, the water repellency of its surface is, at its best, a contact angle of about 100 to 125 degrees by a water droplet method, and has a satisfactory water repellency. It is hard to say that.

[0004] Also, JP-A-4-283268 discloses that
By composite plating using low molecular weight PTFE particles,
It has been proposed to form a highly water-repellent plating film.
However, the plating film obtained by this method is
The reproducibility of the property of high water repellency is poor, and even if the initial water repellency is excellent, there is a disadvantage that the water repellency is remarkably reduced with time when left in air at room temperature.

[0005] On the other hand, an ice producing apparatus used for packing ice, such as fresh fish and fresh food, usually sprays water adhering to the surface of an ice making plate whose outer surface is cooled by an internal refrigerant to thereby lower the adhering water. Freeze to make ice. Conventionally, the surface of an ice making plate is heated or a drug such as ethylene glycol is mixed into water to be sprinkled, in order to improve the ice releasability of the manufactured ice from the ice making container. . And a method of coating a fluororesin such as PTFE having high water repellency and releasability as described above on the metal surface in order to further improve the ice releasability;
As a mobile ice-making container used in a home refrigerator, a method using an ice-making container formed by molding a highly water-repellent resin such as a fluorine-based resin is also performed.

However, the resin coating layer of PTFE or the like has a low thermal conductivity of a fluororesin of about 300 times lower than that of metal and a low strength of the resin itself. There is a disadvantage that the heat transfer speed of the ice making plate is reduced and the ice making efficiency is remarkably reduced because it is necessary to increase the thickness of the ice making plate.

[0007]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a composite plating film having excellent durability, lower surface energy and higher water repellency, and a method for producing the same.

It is a further object of the present invention to provide an ice making plate which is more excellent in ice releasability without lowering the ice making efficiency.

[0009]

Means for Solving the Problems In view of the above-mentioned problems of the prior art, the inventor of the present invention has conducted intensive studies, and as a result, formed a composite plating film containing dispersed fine pitch fluoride particles on a substrate material. When heat treatment is performed at a specific temperature after the heat treatment, the water repellency (by the water droplet method) of the surface of the composite plating film is surprisingly 135 degrees or more, which is considered to be the measurement limit. It has been found that the temperature may exceed 145 degrees.

When the composite plating film is formed on an ice making plate, the ice repellency is greatly improved due to the low surface energy exhibited by the high water repellency, and the metal component originates from the metal component. It has been found that due to the high thermal conductivity, the ice making efficiency is also significantly improved.

Further, together with the pitch fluoride fine particles, at least one of graphite fluoride, PTFE, tetrafluoroethylene-hexafluoropropylene copolymer (FEP) and tetrafluoroethylene-perfluoroalkylvinyl ether copolymer (FEP) When a heat treatment is performed at a specific temperature in the same manner as described above after forming a composite plating film containing dispersed fine particles, the water repellency (by a water droplet method) of the surface of the composite plating film is 120 ° or more. Was found to be improved. And they found that a substrate material provided with such a composite plating film containing two or more kinds of fine particles dispersed therein also exhibited excellent performance as an ice making plate.

That is, the present invention provides a substrate provided with the following composite plating film, a method for producing the same, and an ice making plate; High durability, containing dispersed fine pitch fluoride particles having an average particle diameter of 2 μm or less and having a contact angle of 135 ° or more in a droplet method using water after heat treatment at a temperature of 150 to 300 ° C.
Substrate material with high water-repellent composite plating film.

2. A composite plating film comprising eutectoid pitch fluoride particles on the surface of a substrate material in an electrolytic plating solution containing a surfactant exhibiting cationicity at the pH of the plating solution and dispersing pitch fluoride particles having an average particle size of 2 μm or less. After formation, heat treatment of the composite plating film at a temperature of 150 to 300 ° C. is a method of forming a highly durable and highly water-repellent composite plating film having a contact angle of 135 ° or more by a water droplet method. Production method.

3. Highly durable and highly water-repellent composite containing dispersed fine pitch fluoride particles having an average particle diameter of 2 μm or less and having a contact angle of 135 ° or more in a droplet method using water after heat treatment at a temperature of 150 to 300 ° C. Ice plate with plated coating.

4. Fluorinated pitch fine particles having an average particle size of 2 μm or less, polytetrafluoroethylene fine particles having an average particle size of 2 μm or less, tetrafluoroethylene-hexafluoropropylene copolymer fine particles, tetrafluoroethylene-perfluoroalkylvinyl ether copolymer fine particles, and fluorinated A highly durable and highly water-repellent composite plating film containing at least one kind of graphite fine particles dispersed therein and having a contact angle of 120 ° or more in a droplet method with water after heat treatment at a temperature of 150 to 350 ° C. Substrate material provided.

5. Containing a surfactant showing cationicity at the pH of the plating solution, and fine pitch fluoride particles having an average particle size of 2 μm or less, polytetrafluoroethylene fine particles having an average particle size of 2 μm or less, tetrafluoroethylene-hexafluoropropylene copolymer fine particles, Pitch fluoride fine particles, polytetrafluoroethylene fine particles, and tetrafluoroethylene fine particles are formed on a substrate material surface in an electrolytic plating solution in which at least one of tetrafluoroethylene-perfluoroalkylvinyl ether copolymer fine particles and graphite fluoride fine particles is dispersed. After forming a composite plating film of eutectoid with at least one of hexafluoropropylene copolymer fine particles, tetrafluoroethylene-perfluoroalkylvinyl ether copolymer fine particles and fluorinated graphite fine particles, at a temperature of 150 to 350 ° C. Composite A method for producing a highly durable and highly water-repellent composite plating film having a contact angle of 120 ° or more in a droplet method using water, comprising heat-treating a tacky film.

6. Fluorinated pitch fine particles having an average particle size of 2 μm or less, polytetrafluoroethylene fine particles having an average particle size of 2 μm or less, tetrafluoroethylene-hexafluoropropylene copolymer fine particles, tetrafluoroethylene-perfluoroalkylvinyl ether copolymer fine particles, and fluorinated A highly durable and highly water-repellent composite plating film containing at least one kind of graphite fine particles dispersed therein and having a contact angle of 120 ° or more in a droplet method with water after heat treatment at a temperature of 150 to 350 ° C. Ice plate provided.

[7] It contains dispersed fluorinated pitch fine particles having an average particle size of 2 μm or less and polytetrafluoroethylene fine particles having an average particle size of 2 μm or less, and has a contact angle in a droplet method using water after heat treatment at a temperature of 150 to 350 ° C. A substrate material provided with a highly durable and highly water-repellent composite plating film having a temperature of 120 degrees or more.

8. The surface of the substrate material in an electrolytic plating solution containing a surfactant exhibiting cationicity at the pH of the plating solution and dispersing fine pitch fluoride particles having an average particle size of 2 μm or less and polytetrafluoroethylene fine particles having an average particle size of 2 μm or less. After forming a composite plating film for eutectoid fine pitch fluoride particles and polytetrafluoroethylene fine particles, heat-treating the composite plating film at a temperature of 150 to 350 ° C. Has a contact angle of 1
A method for producing a highly durable and highly water-repellent composite plating film having a temperature of 20 degrees or more.

9. Pitch fluoride fine particles having an average particle size of 2 μm or less and tetrafluoroethylene having an average particle size of 2 μm or less
Highly durable and highly water-repellent composite plating film containing hexafluoropropylene copolymer fine particles dispersed therein and having a contact angle of 120 ° or more in a droplet method with water after heat treatment at a temperature of 150 to 300 ° C. Substrate material with

10. Electroplating containing fine particles of pitch fluoride having an average particle size of 2 μm or less and fine particles of a tetrafluoroethylene-hexafluoropropylene copolymer having an average particle size of 2 μm or less containing a surfactant exhibiting cationicity at the pH of the plating solution. After forming a composite plating film for eutecting pitch fluoride fine particles and tetrafluoroethylene-hexafluoropropylene copolymer fine particles on the surface of a substrate material in a liquid, the composite plating film is heat-treated at a temperature of 150 to 300 ° C. A method for producing a highly durable, highly water-repellent composite plating film having a contact angle of 120 degrees or more in a droplet method using water.

11. A liquid containing water after heat treatment at a temperature of 150 to 340 ° C., containing dispersed fine pitch fluoride particles having an average particle size of 2 μm or less and tetrafluoroethylene-perfluoroalkylvinyl ether copolymer fine particles having an average particle size of 2 μm or less. A substrate material provided with a highly durable and highly water-repellent composite plating film having a contact angle of 120 ° or more by a drop method.

12. Electrolysis in which fine particles of pitch fluoride having an average particle size of 2 μm or less and fine particles of a tetrafluoroethylene-perfluoroalkylvinyl ether copolymer having an average particle size of 2 μm or less containing a surfactant exhibiting cationicity at the pH of the plating solution are dispersed. After forming a composite plating film for eutectoid pitch fluoride fine particles and fine particles of tetrafluoroethylene-perfluoroalkylvinyl ether copolymer on the surface of the substrate material in the plating solution, 150-340 ° C.
A method for producing a highly durable and highly water-repellent composite plating film having a contact angle of 120 ° or more by a water droplet method, wherein the composite plating film is heat-treated at a temperature of:

The pitch fluoride used in the present invention is disclosed in, for example, JP-A-62-275190, and is obtained by fluorinating the pitch using fluorine gas.

In general, the pitch has a layer structure in which aromatic condensed six-membered ring planes are laminated, and has a structure in which aromatics constituting the six-membered ring planes are cross-linked by an aliphatic hydrocarbon group such as methylene. ing. As a raw material for producing pitch fluoride,
Petroleum distillation residue, naphtha pyrolysis residue, ethylene bottom oil,
Examples include pitches obtained by distilling petroleum-based or coal-based heavy oils such as coal liquefied oil and coal tar to remove low-boiling components having a boiling point of less than 200 ° C., and pitches obtained by heat-treating and / or hydrogenating the pitch. You. More specifically, pitch as a raw material for producing fluorinated pitch includes, for example, isotropic pitch, mesophase pitch, hydrogenated mesophase pitch, and distillation of petroleum or coal heavy oil to remove low boiling components. And mesocarbon microbeads composed of mesophase spheres formed after the formation.

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, as a method for producing pitch fluoride, the following method is exemplified.

(1) The raw material pitch and the fluorine gas are 0 to 3
A method of directly reacting at a temperature of about 50 ° C.

The preferred temperature for reacting the pitch with the fluorine gas is a temperature lower than the softening point of the pitch. The fluorine gas pressure during the reaction is not particularly limited,
Generally, it is in the range of 0.07 to 1.5 atmospheres. In this reaction, fluorine gas may be used as it is, or may be diluted with an inert gas such as nitrogen, helium, argon, or neon.

The obtained fluorinated pitch substantially consists of carbon atoms and fluorine atoms, and the F / C atomic ratio is, for example, about 0.5 to 1.8. Such a fluorinated pitch exhibits the following characteristics (a), (b), (c) and (d).

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

(B) In X-ray photoelectron spectroscopy, 29
A peak corresponding to a CF group at 0.0 ± 1.0 eV and 2
A peak corresponding to a CF2 group is shown around 92.5 ± 0.9 eV, and the ratio of the intensity of the peak corresponding to the CF2 group to the peak corresponding to the CF group is about 0.15 to 1.5.

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

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

The fluorinated pitch of the above (1) is a white to yellow-white or brown solid, is excellent in water resistance and chemical resistance, and is a very stable compound.

Further, the fluorinated pitch can be obtained in the form of a transparent resin. Such a transparent resin-like pitch fluoride, for example, the pitch fluoride in a fluorine gas containing atmosphere,
About 0.1 to 3 ° C / min, preferably 0.5 to 1.5 ° C / minute
Temperature to about 250-400 ° C at a rate of about
A predetermined time, for example, about 1 to 18 hours, preferably 6 to
It is obtained by reacting for about 12 hours. The obtained transparent resinous fluoride pitch exhibits, for example, the following characteristics.

F / C: 1.5 to 1.7 Light transmittance (250 to 900 nm): 90% or more Molecular weight: 1500 to 2000 Softening point: 150 to 250 ° C. In the present invention, the above-mentioned pitch fluoride is further used. At least a part (up to about 90%) of the fine particles can be replaced by at least one of PTFE fine particles, FEP fine particles, PFA fine particles and fluorinated graphite fine particles having an average particle diameter of 2 μm or less. In this case, although the water repellency is slightly lowered, there is obtained an advantage that durability, slidability, antifouling property, burning resistance and the like are improved by appropriately selecting an alternative. Even when a part of the pitch fluoride fine particles is replaced with these materials, the particle diameter, the amount of the fine particles in the composite plating film, the method of forming the composite plating film, etc. do not substantially change. In the following, unless otherwise required, fine pitch fluoride particles will be described as a typical example.

In forming the eutectoid composite plating in the present invention, a known electroless plating method and an electrolytic plating method capable of depositing a matrix metal on the surface of a substrate material such as a metal used as an ice making plate or the like may be employed. it can. As for the plating solution to be used, any of various plating solutions having a known composition can be used. More specifically, for example, JP-A-49-27443 and JP-A-4-32
According to the plating method disclosed in, for example, Japanese Patent No. 9897, the pitch fluoride fine particles are dispersed in an aqueous solution of a plating metal salt, and the pitch fluoride fine particles are co-deposited with a matrix metal on a substrate plate. What is necessary is just to form a composite plating film having both the intrinsic properties of a certain fluorocarbon compound and the properties of a metal as a matrix.

The metal used as a salt in the plating bath and serving as a matrix in the composite plating film is, for example, nickel, copper, zinc, tin, iron, lead, cadmium, or the like.
Any of chromium, precious metals, and alloys thereof can be used. Various plating compositions containing these metals are known. In the present invention, any of these known plating solutions can be used.

In the present invention, the particle size of the fine pitch fluoride particles added to the plating solution for forming the composite plating film (hereinafter, referred to as the composite plating solution) is not particularly limited, but the total particle size of the composite plating film is not particularly limited. If the thickness is larger than the film thickness, the particles fall off the plating surface due to friction. Therefore, it is desirable to use fine particles smaller than the plating film thickness. The thickness of the composite plating film according to the present invention varies depending on the material, use and shape of the substrate material, the type of the matrix metal, and the like, but is usually about 1 to 50 μm. Accordingly, the particle size of the fine pitch fluoride particles may be determined in consideration of the thickness of the composite plating film, but is usually about 2 μm on average, and more preferably 1 μm or less on average. Further, in order to ensure the uniformity of dispersion of the fine pitch fluoride particles in the composite plating solution and the composite plating film, it is desirable not to include coarse particles of 30 μm or more. The addition amount of the fine pitch fluoride particles in the composite plating solution is not particularly limited,
Usually about 200 g / l or less, preferably 1 to 100 g / l
It is about l. Even when part of the fluorinated pitch fine particles is replaced with PTFE fine particles or the like, the total amount of addition is the same.

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, considering the adhesion between the plating film and the substrate material,
The volume fraction of eutectoids (fine pitch fluoride particles) in the composite plating film is limited to 60%. On the other hand, when the volume fraction of the fluorinated pitch fine particles is too low, the water repellency is not sufficiently improved. Therefore, in the present invention, the volume fraction of fine pitch fluoride particles in the composite plating film is usually 2%.
It is about 5 to 50%, more preferably about 35 to 45%. The quantitative value of the eutectoid is the same when a mixture of fine pitch fluoride particles and other fine particles is used.

In the present invention, the substrate material is copper,
Metals such as stainless steel, general steel, aluminum and aluminum alloys, resins such as PTFE, carbon plates,
A carbon material such as a graphite plate is used. When the substrate material according to the present invention is used as a member for a cooking utensil (for example, a top plate), carbon materials and metals having high heat conductivity and high heat resistance are preferred. When used as a substrate material for an ice making plate, a metal having high thermal conductivity is preferable, and a copper plate, an aluminum plate, an aluminum alloy plate and the like are more preferable.

In the composite plating solution for forming the composite plating film of the present invention, it is necessary to uniformly disperse pitch fluoride fine particles having extremely high water repellency in the plating solution and to make them completely wet. And a surfactant. As the surfactant, for example, a water-soluble cationic or nonionic surfactant or an amphoteric surfactant that exhibits cationicity at the pH value of the plating solution can be used. In this case, examples of the cationic surfactant include quaternary ammonium salts and secondary and tertiary amines, and examples of the nonionic surfactant include polyoxyethylene, polyethyleneimine, and ester-based surfactants. And the like. Examples of the amphoteric surfactant include carboxylic acid-based and sulfone-based surfactants. In particular, it is preferable to use a fluorinated surfactant having a CF bond in the molecule.

The amount of the surfactant to be added to the plating solution is usually in the range of about 1 to 100 mg, more preferably about 1 to 50 mg, per 1 g of the fine pitch fluoride particles.

In the present invention, known additives such as a primary brightener, a secondary brightener, and a pigment for coloring a plating film can be further added to the composite plating solution.

In forming a composite plating film by the method of the present invention, it is preferable to perform a plating operation while stirring the composite plating solution in order to uniformly disperse the fine pitch fluoride particles. The stirring method is not particularly limited, and a usual mechanical stirring means, for example, a method of screw stirring, a method of stirring with a magnetic stirrer, or the like can be employed.

The plating conditions are determined by the temperature of the solution and pH within the same ranges as those generally employed in the ordinary composite plating method, depending on the material of the substrate material, the type of the composite plating solution to be used, and the like.
What is necessary is just to select from values, current density, etc.

In the present invention, the composite plating film is
It is not always necessary to form directly on the substrate material, and a known base plating layer (for example, nickel plating,
After forming copper plating, a composite plating film may be formed.

In the present invention, it is essential that the composite plating film formed on the substrate material as described above is heat-treated within a temperature range of 150 to 350 ° C. In some cases, it is preferable to slightly lower the upper limit of the heat treatment temperature within this range. For example, when using pitch fluoride alone or when using pitch fluoride and FEP together, it is preferable to perform the heat treatment at a temperature of 300 ° C. or lower. Further, when using pitch fluoride and PFA together, it is preferable to perform the heat treatment at a temperature of 340 ° C. or lower.

By this heat treatment, the durability and the surface water repellency of the composite plating film are remarkably improved, and when the fine pitch fluoride particles are solely co-deposited, the contact angle of the droplet method with water becomes 135 ° or more. In some cases, and may exceed the limit of 145 degrees, which is considered to be the limit of measurement by this method. When the pitch fluoride and other fine particles are used in combination, the contact angle in the droplet method using water is improved to 120 degrees or more. It is not clear why this heat treatment significantly improves the water repellency of the composite plating film. However, wetting due to thermal modification of the composite plating film itself and removal of surfactants (due to thermal decomposition, evaporation, sublimation, etc.) It is inferred that the decline in gender also contributes to this. The heat treatment time is not particularly limited, but may be generally about 10 to 30 minutes. If the heat treatment temperature is lower than 150 ° C., it is necessary to lengthen the processing time in order to obtain a sufficient processing effect, while if it is higher than 350 ° C., the plating film may be deteriorated.

In the present invention, eutectoid components can be selected according to the use of the substrate material and the like. For example, when high heat resistance is required, pitch fluoride and PTFE
In the case where high water repellency is required, a mixture of pitch fluoride alone or pitch fluoride and PTFE is preferred.
And / or a mixed system with FEP (in which the content of pitch fluoride is increased) is preferable. Furthermore, in order to improve antifouling property, scoring resistance, deicing property, slidability, etc., a mixed system (P) of fluorinated pitch and PTFE and / or FEP is used.
Those having an increased content of TFE and / or FEP) are preferred.

[0051]

The composite plating film formed on the substrate material according to the present invention has both the unique properties of the non-metallic pitch fluoride and the unique properties of the matrix metal.
More specifically, this composite plating film firstly has a high degree of lubrication derived from pitch fluoride, abrasion resistance, etc.
Furthermore, it exhibits particularly excellent durability and water repellency.

The composite plating film further has high hardness, high strength, high thermal conductivity, high electrical conductivity, and the like derived from the matrix metal, and exhibits excellent adhesion to the substrate material. Therefore, the composite plating film according to the present invention is superior in strength and is less likely to be scratched, compared to a coating film of a fluororesin such as PTFE or a fluororesin molded product.
It is hard to separate from the substrate material and has excellent thermal conductivity and durability.

When the pitch fluoride fine particles are used in combination with other fine particles such as PTFE, the water repellency is slightly reduced, but the durability is improved, and other effects similar to the above are obtained. .

As a result, when an ice making plate is formed from a substrate material having a composite plating film according to the present invention, the ice separating property and the ice making efficiency are greatly improved, and the durability of the ice making container is improved.

Further, the substrate material having the composite plating film according to the present invention is useful as a material for a wide range of uses other than an ice-making plate by utilizing water repellency or various other excellent properties in addition to water repellency. is there. Some examples of these uses are: oil repellency, antifouling properties, heat resistant scorchability ... inside of dishwasher, inside of washing machine tank, range hood, ventilation fan, table stove top, table stove juice Saucer, oven dish, iron plate for roasted meat, rostrole, Genghis Khan pot, frying pan,
Like, grill, gas stove, oven, microwave,
Rice cookers, barbecue stoves, hot plates, pots, oven toasters, electric pots, electromagnetic induction heaters, system kitchen tops, sinks, faucets, mixing faucets, gas pipe inner and outer coats, etc. In particular, when the fine particles of pitch fluoride and other fine particles such as PTFE are dispersed together, more excellent results are obtained in terms of antifouling property, heat-resistant scoring property and the like.

-Dew condensation prevention property: interior of bathroom, etc.

-Water repellency and antifouling properties-Bathtub-Thermal conductivity-Exhaust top, heat exchanger fins, carbon fiber surface coat, carbon material coat, LNG vaporizer evaporator, copy roller, etc.

-Releasability: molds and the like.

-Water repellency and ice releasability: parts for aircraft and helicopters-Sliding property: gas valve inner surface coating, etc. In particular, when the fine pitch fluoride particles and other fine particles such as PTFE are dispersed together, the effect is remarkably improved.

[0060]

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 0.2% 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.

Then, nitrogen gas was introduced into the obtained reduced pitch to remove low molecular weight components, followed by thermal polymerization at 450 ° C. for 5 hours, softening point 300 ° C., quinoline insoluble content 60% by weight, benzene insoluble content 98% by weight. %, And a mesophase pitch having a mesophase content of 90% by weight or more was obtained.

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 650 cc / min and reacted for 20 hours. As a result, 144 g of pitch fluoride particles were obtained. As a result of elemental analysis, the composition formula was CF _1.38 , and the average particle size was 10 μm.
m.

Example 1 5% by weight of finely pulverized pitch fluoride particles (average particle size: 1.3 μm) obtained in Reference Example 1 were added to a nickel electrolytic bath having the following composition. As a surfactant, a tertiary perfluoroammonium salt (trademark "Megafac F-15")
0 ”, manufactured by Dainippon Ink and Chemicals, Inc., (C ₈ F ₁₇ SO ₂ NH
(CH ₂ ) ₃ N ⁺ (CH ₃ ) ₃ .Cl ⁻ )} was added at a ratio of 30.0 mg to 1 g of pitch fluoride.

Nickel sulfamate electrolytic bath composition Nickel sulfamate 350 g / l Nickel chloride 45 g / l Boric acid 40 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 45 ± 5.
C, pH 4.2, current density 3 or 5 A / dm ² ,
Electroplating was performed with a screw stirring until the film thickness became 10 μm to form a nickel-fluoride pitch composite plating film.

The obtained copper plate having a nickel-fluoride pitch composite plating film was vacuum-dried, and then dried at 250 ° C. for 30 minutes.
After heating for 1 minute and leaving the room indoors at room temperature for 1 hour and 3 months, a droplet was measured using a FACE contact angle meter (“CA-A type”, manufactured by Kyowa Interface Science Co., Ltd.). The contact angle of water was measured by the method, and its water repellency was examined. Table 1 shows the results. Table 1 also shows the results of Examples 2 to 6 and Comparative Examples 1 to 7. However,
For Comparative Examples other than Examples 2 and 4 and Comparative Example 2,
Only the results for one hour after the heat treatment are shown.

Comparative Example 1 A nickel-fluoride pitch composite plating film was formed on a copper plate in the same manner as in Example 1 except that the plating film was not subjected to vacuum drying and heat treatment.

Comparative Example 2 A nickel electrolytic bath having the following composition was prepared using tetrafluoroethylene oligomer particles having an average particle size of 4 μm (manufactured by Central Glass Co., Ltd.), and 0.1 mm in the following conditions.
× 30mm × 30mm copper plate with composite plating film (film thickness 1
0 μm).

Nickel electrolytic bath composition Nickel sulfamate 350 g / l Nickel chloride 45 g / l Boric acid 40 g / l Surfactant (trade name "Megafac F-150", manufactured by Dainippon Ink and Chemicals, Inc.) 0.5 g / l plating Conditions pH 3.7 Temperature 43 ° C. Cathode current density 5 A / dm ² Anode Nickel plate Stirring Ultrasonic time 10 minutes Example 2 Using a wood bath having the following composition, liquid temperature 25 ° C., current density 10 A / dm ² 0.5 mm x 3 cm x 5 cm of stainless steel (SUS3
04) was subjected to nickel plating.

Wood bath composition Nickel chloride: 245 g / l Hydrochloric acid: 120 g / l Then, a nickel-fluoride pitch composite plating film was formed on the nickel-plated stainless steel in the same manner as in Example 1 except that the above-mentioned nickel-plated stainless steel was used as a negative electrode. Was formed and heat treated, and the water repellency of the film was examined.

Example 3 Finely pulverized particles of fluorinated pitch obtained in Reference Example 1 (average particle diameter: 1.3 μm) 1.25% by weight and FEP fine particles (average particle diameter: 0.2 to 0.3 μm; Daikin Industries, Ltd.) Co., Ltd.) was dispersed in the same nickel plating bath as used in Example 1. At this time, 1 g of fluorinated pitch and PTFE
For 1 g, use a surfactant (trade name "MegaFac F-15").
0 ", manufactured by Dainippon Ink and Chemicals, Inc.)
And 65 mg in advance.

Next, in the same manner as in Example 2,
0.5mm × 3c with μm nickel plating coating
Using a stainless steel plate of mx 5 cm as a negative electrode and a nickel plate as a positive electrode under the conditions of a liquid temperature of 45 ± 5 ° C, a pH of 3.8 to 4.2, a current density of 3 or 5 A / dm ² until the film thickness becomes 10 μm. Electroplating was performed to form a nickel-fluoride pitch-FEP composite plating film.

The obtained nickel-fluoride pitch-FEP
The stainless steel sheet having the composite plating film was treated in the same manner as in Example 1 except that the stainless steel plate was heated at 250 ° C. for 30 minutes using a hot air drier, and the water repellency of the film was measured.

Example 4 Finely pulverized pitch fluoride particles (average particle diameter 1.3 μm) of 5% by weight and low molecular weight PTFE fine particles (average particle diameter of about 0.5 μm; trade name “Sephrallube V”) obtained in Reference Example 1 ,
1.25% by weight (manufactured by Central Glass Co., Ltd.) was dispersed in the same nickel plating bath as used in Example 1. At this time, for 1 g of fluorinated pitch and 1 g of PTFE,
A surfactant (trade name “MegaFac F-150”, manufactured by Dainippon Ink and Chemicals, Inc.) was previously mixed at a ratio of 30 mg and 65 mg, respectively.

Using the obtained nickel plating bath, a nickel-fluoride pitch-PTFE composite plating was carried out in the same manner as in Example 3 on a stainless steel plate on which a nickel plating film having a thickness of 2 μm was previously formed as in Example 2. After forming the coating, the coating was treated in the same manner as in Example 1 except that the coating was heated at 250 ° C. for 30 minutes using a hot air drier, and the water repellency of the coating was measured.

Example 5 Fine particles of pitch fluoride obtained in Reference Example 1 (average particle diameter: 1.3)
μm) 1.25% by weight and PTFE fine particles (particle size 2 μm)
m or less, manufactured by Daikin Industries, Ltd.), and a surfactant (trade name “MegaFac F-150”, manufactured by Dainippon Ink and Chemicals, Inc.) is used for 1 g of fluorinated pitch and 1 g of PTFE. The same procedure as in Example 1 was carried out except that a plating bath added at a ratio of 30 mg and 30 mg, respectively, was used.
A PTFE composite plating film was formed.

The obtained nickel-fluoride pitch-PTF
The stainless steel plate having the E composite plating film was treated in the same manner as in Example 1 except that the stainless steel plate was heated at 250 ° C. for 30 minutes using a hot air drier, and the water repellency of the film was measured.

Example 6 Fine particles of pitch fluoride obtained in Reference Example 1 (average particle diameter: 1.3)
μm) 1.25% by weight and PFA fine particles (particle size 2 μm
Hereinafter, 5% by weight of Daikin Industries, Ltd.) is used, and a surfactant (trade name “MegaFac F-150”, manufactured by Dainippon Ink and Chemicals, Inc.) is used for 1 g of fluorinated pitch and 1 g of PFA, respectively. Except for using a plating bath added at a ratio of 30 mg and 30 mg, in the same manner as in Example 1 and in the same manner as in Example 2 on a stainless steel plate on which a nickel plating film having a thickness of 2 μm was previously formed.
A PFA composite plating film was formed.

The obtained nickel fluoride pitch-PFA
The stainless steel sheet having the composite plating film was treated in the same manner as in Example 1 except that the stainless steel plate was heated at 250 ° C. for 30 minutes using a hot air drier, and the water repellency of the film was measured.

Comparative Example 3 The powder of pitch fluoride obtained in Reference Example 1 (average particle size: 10 μm)
m) was used in the same manner as in Example 1 except that
After obtaining a copper plate having a fluorinated pitch composite plating film, it was heat-treated and its water repellency was examined.

COMPARATIVE EXAMPLE 4 A copper plate having a nickel-fluorinated graphite composite plating film was obtained in the same manner as in Example 1 except that fluorinated graphite fine particles having an average particle size of 1 μm were used instead of the fluorinated pitch fine particles.
After heat treatment, its water repellency was examined. However, 1g of fluorinated graphite
The amount of the surfactant was 40 mg.

Comparative Example 5 A PT having an average particle size of 3.5 μm was used in place of the fine pitch fluoride particles.
Except that FE is used, nickel-
After obtaining a copper plate having a PTFE composite plating film, it was heat-treated and its water repellency was examined. However, the amount of the surfactant added was 4.5 mg per 1 g of PTFE.

Comparative Example 6 A nickel plating film was formed on a copper plate in the same manner as in Example 1 except that no pitch fluoride was used.

Comparative Example 7 The water repellency of a copper plate on which no nickel plating film was formed was measured.

[0085]

[Table 1]

From the results shown in Table 1, it is clear that the pitch fluoride eutectoid composite plating film of the present invention has extremely excellent water repellency.

Example 7 1 cc of distilled water was gently dropped with a syringe onto the surface (3 cm × 5 cm) of the two types of nickel-fluoride pitch composite plated copper plates obtained in Example 1, and the diameter was 2.1 cm. Was left in an ice making room at −20 ° C. for 3 hours to freeze the water droplets. Next, the plating-coated copper plate was quickly taken out of the ice-making room, allowed to stand vertically in a constant temperature room at 17 ° C., and the time until the drop (slipping) of ice droplets was measured. Table 2 shows the results. Table 2 shows Examples 8 to 10 and Comparative Examples 8 to
9 are also shown.

Example 8 The same experiment as in Example 7 was performed using the two types of composite plated copper plates obtained in Example 3.

Example 9 The same experiment as in Example 7 was performed using the two types of composite plated copper plates obtained in Example 5.

Example 10 An experiment similar to that of Example 7 was performed using the two types of composite plated steel sheets obtained in Example 6.

COMPARATIVE EXAMPLE 8 The ice-peeling test was performed on the nickel-plated copper plate obtained in Comparative Example 6 in the same manner as in Example 7.

Comparative Example 9 A copper plate having no nickel plating film as in Comparative Example 7 was subjected to a deicing test in the same manner as in Example 7.

[0093]

[Table 2]

From the results shown in Table 2, it is clear that the eutectoid composite plating film containing fine pitch fluoride particles according to the present invention has extremely excellent ice-repelling properties.

Example 11 Electroplating was carried out in the same manner as in Example 1 except that a steel sheet of 0.5 mm × 3 cm × 5 cm was used as a negative electrode to form a steel sheet having a nickel-fluoride pitch composite plating coating. Heat treatment was performed in the same manner as in Example 1, and the contact angle was measured. In this case, the same excellent water repellency and durability as in Example 1 were obtained.

Example 12 Fine particles of pitch fluoride obtained in Reference Example 1 (average particle diameter 1.3)
μm) 1.25% by weight, PTFE fine particles (particle size 2 μm or less, manufactured by Daikin Industries, Ltd.) 2.5% by weight and FEP
Fine particles (particle size 0.2-0.3 μm, Daikin Industries, Ltd.)
2.5% by weight and 1 g of fluorinated pitch, P
Surfactant (trade name "MegaFac F-150", manufactured by Dainippon Ink and Chemicals, Inc.) for 1 g of TFE and 1 g of FEP
In the same manner as in Example 1 except that a plating bath containing 30 mg, 30 mg, and 65 mg, respectively, was added on a stainless steel plate on which a nickel plating film having a thickness of 2 μm had been formed in the same manner as in Example 2. Chemical pitch-
A PTFE-FEP composite plating film was formed.

The obtained nickel-fluoride pitch-PTF
A stainless steel plate having an E-FEP composite plating film was treated in the same manner as in Example 1 except that the stainless steel plate was heated at 250 ° C. for 30 minutes using a hot air drier, and the water repellency of the film was measured.

In this case, the same excellent water repellency and durability as in Example 1 were obtained.

Example 13 Fine particles of pitch fluoride obtained in Reference Example 1 (average particle diameter: 1.3)
μm) 1.25% by weight, PTFE fine particles (particle size 2 μm or less, manufactured by Daikin Industries, Ltd.) 2.5% by weight and PFA
1. Fine particles (particle size: 2 μm or less, manufactured by Daikin Industries, Ltd.)
5% by weight, 1 g of fluorinated pitch, PTFE1
Example 1 except that a plating bath containing 30 mg, 30 mg and 30 mg of a surfactant (trade name “MegaFac F-150”, manufactured by Dainippon Ink and Chemicals, Inc.) was used for each g and 1 g of PFA, respectively. Pitch fluoride-PTFE on a stainless steel plate on which a nickel plating film having a thickness of 2 μm was previously formed in the same manner as in Example 2.
-PFA composite plating film was formed.

The obtained nickel-fluoride pitch-PTF
A stainless steel plate having an E-PFA composite plating film was treated in the same manner as in Example 1 except that the stainless steel plate was heated at 250 ° C. for 30 minutes using a hot air drier, and the water repellency of the film was measured.

In this case, the same excellent water repellency and durability as in Example 1 were obtained.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C25D 15/02 C08L 101/00 F25C 1/12

Claims (12)

(57) [Claims] 1. High durability containing dispersed fine pitch fluoride particles having an average particle diameter of 2 μm or less, and having a contact angle of 135 ° or more in a droplet method using water after heat treatment at a temperature of 150 to 300 ° C.・ Substrate material with high water-repellent composite plating film. 2. A fine pitch fluoride particle is co-deposited on the surface of a substrate material in an electrolytic plating solution containing a surfactant exhibiting cationicity at the pH of a plating solution and having a mean particle size of 2 μm or less dispersed therein. After the formation of the composite plating film to be formed, the composite plating film is heat-treated at a temperature of 150 to 300 ° C., and has a contact angle of 135 ° or more in a droplet method using water. A method for producing an aqueous composite plating film. 3. A highly durable powder containing fine pitch fluoride particles having an average particle diameter of 2 μm or less dispersed therein and having a contact angle of 135 ° or more in a droplet method using water after heat treatment at a temperature of 150 to 300 ° C. -An ice making plate with a highly water-repellent composite plating film. 4. Fine particles of pitch fluoride having an average particle diameter of 2 μm or less, fine particles of polytetrafluoroethylene having an average particle diameter of 2 μm or less, fine particles of a tetrafluoroethylene-hexafluoropropylene copolymer, and copolymers of tetrafluoroethylene-perfluoroalkylvinyl ether. High durability and high repellency which contain at least one of coalesced fine particles and fluorinated graphite fine particles in a dispersed state and have a contact angle of 120 ° or more in a droplet method with water after heat treatment at a temperature of 150 to 350 ° C. Substrate material with aqueous composite plating film. 5. Fine particles of pitch fluoride having an average particle diameter of 2 μm or less, fine particles of polytetrafluoroethylene having an average particle diameter of 2 μm or less, and tetrafluoroethylene-hexafluoropropylene containing a surfactant exhibiting cationicity at the pH of the plating solution. Pitch fluorinated fine particles and polytetrafluoroethylene fine particles on the surface of a substrate material in an electrolytic plating solution in which at least one of copolymer fine particles, tetrafluoroethylene-perfluoroalkylvinyl ether copolymer fine particles and fluorinated graphite fine particles are dispersed. After forming a composite plating film eutectoid with at least one of tetrafluoroethylene-hexafluoropropylene copolymer fine particles, tetrafluoroethylene-perfluoroalkylvinyl ether copolymer fine particles and fluorinated graphite fine particles,
The composite plating film is heat-treated at a temperature of 150 to 350 ° C., and has a contact angle of 120 by a water droplet method.
A method for producing a highly durable and highly water-repellent composite plating film having a degree or higher. 6. Fine particles of pitch fluoride having an average particle size of 2 μm or less, fine particles of polytetrafluoroethylene having an average particle size of 2 μm or less, fine particles of a tetrafluoroethylene-hexafluoropropylene copolymer, and a copolymer of tetrafluoroethylene-perfluoroalkylvinyl ether. High durability and high repellency which contain at least one of coalesced fine particles and fluorinated graphite fine particles in a dispersed state and have a contact angle of 120 ° or more in a droplet method with water after heat treatment at a temperature of 150 to 350 ° C. An ice making plate with an aqueous composite plating film. 7. A droplet method using water containing dispersed fine pitch fluoride particles having an average particle size of 2 μm or less and polytetrafluoroethylene particles having an average particle size of 2 μm or less, and heat-treated at a temperature of 150 to 350 ° C. A substrate material provided with a highly durable and highly water-repellent composite plating film having a contact angle of not less than 120 degrees. 8. An electrolytic plating solution containing a surfactant exhibiting cationicity at the pH of the plating solution, and dispersed therein fine pitch fluoride particles having an average particle size of 2 μm or less and polytetrafluoroethylene fine particles having an average particle size of 2 μm or less. After forming a composite plating film for eutectoid pitch fluoride particles and polytetrafluoroethylene particles on the substrate material surface in
A method for producing a highly durable and highly water-repellent composite plating film having a contact angle of 120 ° or more by a water droplet method, wherein the composite plating film is heat-treated at a temperature of 50 to 350 ° C. 9. Dispersed fine pitch fine particles having an average particle size of 2 μm or less and fine particles of a tetrafluoroethylene-hexafluoropropylene copolymer having an average particle size of 2 μm or less are dispersed and heat-treated at a temperature of 150 to 300 ° C. A substrate material provided with a highly durable and highly water-repellent composite plating film having a contact angle of 120 ° or more in a droplet method using water. 10. A fluorinated pitch fine particle having an average particle size of 2 μm or less and a tetrafluoroethylene-hexafluoropropylene copolymer fine particle having an average particle size of 2 μm or less containing a surfactant exhibiting a cationic property at the pH of a plating solution. After forming a composite plating film of eutectoid pitch fluoride fine particles and tetrafluoroethylene-hexafluoropropylene copolymer fine particles on the substrate material surface in the dispersed electrolytic plating solution, the composite is formed at a temperature of 150 to 300 ° C. A method for producing a highly durable and highly water-repellent composite plated film having a contact angle of 120 ° or more by a water droplet method, wherein the plated film is heat-treated. 11. A dispersion containing fine pitch fine particles having an average particle diameter of 2 μm or less and fine particles of a tetrafluoroethylene-perfluoroalkylvinyl ether copolymer having an average particle diameter of 2 μm or less, and heat-treated at a temperature of 150 to 340 ° C. A substrate material provided with a highly durable and highly water-repellent composite plating film having a contact angle of 120 ° or more by a droplet method using water later. 12. A fluorinated pitch fine particle having an average particle size of 2 μm or less and a tetrafluoroethylene-perfluoroalkylvinyl ether copolymer fine particle having an average particle size of 2 μm or less containing a surfactant exhibiting cationicity at the pH of a plating solution. After forming a composite plating film of eutectoid pitch fluoride fine particles and tetrafluoroethylene-perfluoroalkylvinyl ether copolymer fine particles on the surface of the substrate material in an electrolytic plating solution in which is dispersed, a temperature of 150 to 340 ° C. A method for producing a highly durable and highly water-repellent composite plating film having a contact angle of 120 ° or more in a droplet method using water, wherein the composite plating film is subjected to a heat treatment.