WO2017013716A1 - Satin finish immersion coating and surface treatment method using same - Google Patents

Satin finish immersion coating and surface treatment method using same Download PDF

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Publication number
WO2017013716A1
WO2017013716A1 PCT/JP2015/070587 JP2015070587W WO2017013716A1 WO 2017013716 A1 WO2017013716 A1 WO 2017013716A1 JP 2015070587 W JP2015070587 W JP 2015070587W WO 2017013716 A1 WO2017013716 A1 WO 2017013716A1
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Prior art keywords
paint
treated
satin
surface treatment
treatment method
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PCT/JP2015/070587
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French (fr)
Japanese (ja)
Inventor
大祐 佐土原
美代子 泉谷
鈴木　啓太
西川　賢一
勝己 下田
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株式会社Ｊｃｕ
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Priority to PCT/JP2015/070587 priority Critical patent/WO2017013716A1/en
Priority to JP2017529189A priority patent/JPWO2017013716A1/en
Publication of WO2017013716A1 publication Critical patent/WO2017013716A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/28—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for wrinkle, crackle, orange-peel, or similar decorative effects
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives

Definitions

  • the present invention relates to a satin paint for dipping and a surface treatment method using the same.
  • a satin color tone by plating for example, a change in the type of brightener added to the plating solution, a composite plating using a plating solution to which fine particles having a small particle diameter are added, or a plating solution to which an emulsion is added is used.
  • Techniques such as satin plating are known.
  • Patent Document 1 proposes a technology to obtain a satin color tone by painting a coating assembled with zinc flakes and a binder on the raw metal, but constantly stirring is necessary due to the problem of liquid stability, There is a problem that the screw portion is clogged when used for a fastening member because of its high viscosity.
  • the object of the present invention is to provide a surface treatment technology that can protect a material without damaging the material, has a high corrosion resistance, and can provide a satin-like color tone with controlled gloss by a simple process. And providing this means.
  • the inventors of the present invention combined a metal flake having a specific size with a silicon oligomer to form a paint, whereby the metal flake was dispersed in the paint and precipitated. Therefore, the present inventors have found that a satin-like color tone can be imparted to an object to be treated by simple dipping, and the present invention has been completed.
  • the present invention is a satin-like paint for immersion characterized by containing metal powder, silicon oligomer, and resin having an average particle diameter of 1 to 50 ⁇ m and an average piece thickness of 5 to 50 nm.
  • the present invention is a surface treatment method characterized by immersing an object to be treated in the above-mentioned dipping satin paint.
  • the present invention is a surface-treated product obtained by immersing an object to be treated in the above-mentioned dipping satin paint.
  • the satin-like paint for immersion of the present invention does not require dispersion of the metal flakes contained therein and does not precipitate, so that stirring of the paint is unnecessary, and a satin-like color tone is uniformly imparted to the object to be treated by immersion. it can
  • the satin-like paint for dipping of the present invention can provide corrosion resistance even with a thinner film thickness than the conventional one, and the number of times of dipping is sufficient. Therefore, it is suitable for use in a large amount of processing such as parts for automobiles.
  • the metal flakes used in the satin paint for immersion of the present invention (hereinafter referred to as “the present paint”) have an average particle diameter of 1 to 50 ⁇ m, preferably 1 to 10 ⁇ m, and an average flake thickness of 5 to 50 nm, preferably 1 to 25 nm.
  • the kind of metal is not particularly limited, and examples thereof include zinc, iron, nickel, copper, and aluminum. Among these, aluminum is the best because it can give a satin color tone.
  • These metal flakes can be used alone or in combination of two or more. Moreover, as such a metal flake, what is obtained by a vapor deposition method etc. according to a conventional method, for example, and a commercial item can be utilized.
  • the average particle diameter is an average value of the particle diameter (long side) of a thin piece of about 5 to 20 measured by an optical microscope, and the average piece thickness is a film of a thin piece of about 5 to 20 observed in an SEM image. Average thickness.
  • the content of the metal flakes in the paint of the present invention is not particularly limited, and is, for example, 0.1 to 10% by mass (hereinafter simply referred to as “%”), preferably 0.3 to 1.0%.
  • the silicon oligomer used in the paint of the present invention is not particularly limited, and examples thereof include alkoxysilane oligomers.
  • This alkoxysilane oligomer is a reaction condensate of alkoxysilane and water or polyhydric alcohol, which is a condensate of the alkoxy group of alkoxysilane and the hydroxy group of water or polyhydric alcohol.
  • the number of silicon atoms in the alkoxysilane oligomer is not particularly limited, but is 2 to 8, for example, more preferably 2 to 4.
  • the alkoxysilane used as the raw material for the alkoxysilane oligomer is not particularly limited, and examples thereof include tetraethoxysilane and tetramethoxysilane.
  • the polyhydric alcohol used as the raw material for the alkoxysilane oligomer is not particularly limited, and examples thereof include ethylene glycol, diethylene glycol, triethylene glycol, and 1,3-butylene glycol.
  • alkoxysilane oligomers are obtained by subjecting alkoxysilane and water or a polyhydric alcohol to a condensation reaction at about 50 ° C. for about 2 hours in the presence of a metal salt as a catalyst, and by not fractionating the alcohol produced during the reaction. can get.
  • the metal salt used as a catalyst is not particularly limited, and examples thereof include aluminum chloride, zinc chloride, and iron chloride.
  • reaction condensates of alkoxysilane and water or polyhydric alcohol the reaction condensate of alkoxysilane and polyhydric alcohol is preferable, and alkoxysilane, ethylene glycol, diethylene glycol, triethylene glycol, 1,3-butylene.
  • a reaction condensate with a dihydric alcohol such as glycol is particularly preferred from the viewpoint of stability when it is used as the coating material of the present invention.
  • reaction condensate of alkoxysilane and a dihydric alcohol such as ethylene glycol, diethylene glycol, triethylene glycol, 1,3-butylene glycol and the like
  • a dihydric alcohol such as ethylene glycol, diethylene glycol, triethylene glycol, 1,3-butylene glycol and the like
  • these pamphlet is particularly preferable.
  • Those described in the examples are preferred.
  • silicon oligomers can be used alone or in combination of two or more.
  • the content of the silicon oligomer in the paint of the present invention is not particularly limited, and is, for example, 0.1% or more, preferably 0.5 to 5.0%.
  • the resin used for the paint of the present invention is not particularly limited, and examples thereof include acrylic resins, urethane resins, phenol resins, epoxy resins and the like. Among these resins, acrylic resins are preferable. Among acrylic resins, methacrylic acid alkyl ester copolymers, colloidal silica / acrylic composites, and ethylene / acrylic acid copolymer ammonium salts are more preferable. Coalescence is particularly preferred. These resins may be used alone or in combination of two or more.
  • the content of the resin in the paint of the present invention is not particularly limited, and is, for example, 0.1 to 50%, preferably 1 to 20%.
  • the pigment of the present invention can further contain a pigment.
  • the pigment used in the paint of the present invention is not particularly limited except that it does not correspond to the above-mentioned metal flakes.
  • metal flakes aluminum, titanium, silicon, barium, zirconium and other metal oxides, sulfates or treated products thereof, etc.
  • examples thereof include pigments derived from these metals, polyolefin resins such as polyethylene and polypropylene, pigments derived from resins such as fluororesins such as polytetrafluoroethylene and tetrafluoroethylene-perfluoroalkyl vinyl ether copolymers, and carbon black.
  • carbon black is preferable.
  • the content of the pigment in the paint of the present invention is not particularly limited, and is, for example, less than 10%, preferably 0.3 to 1.0%.
  • the paint of the present invention may contain a friction coefficient adjusting agent, a film thickener and the like as long as the effects of the present invention are not impaired.
  • the friction coefficient adjusting agent is not particularly limited, and examples thereof include polyethylene wax.
  • the film thickener is not particularly limited, and examples thereof include fumed silica.
  • the viscosity of the paint of the present invention may be adjusted by appropriately diluting with a high boiling point solvent such as 1-methoxy-2-propanol, isopropyl alcohol or the like.
  • a high boiling point solvent such as 1-methoxy-2-propanol, isopropyl alcohol or the like.
  • the viscosity of the paint of the present invention is not particularly limited, but is, for example, 5 to 15 mPa ⁇ s, preferably 7 to 10 mPa ⁇ s.
  • ⁇ Titanium color> Aluminum flakes (average particle size 10-15 ⁇ m, average piece thickness 5-15 nm) 0.3-10% Acrylic ester copolymer 1-50% Alkoxysilane oligomer * 0.5-5.0% Isopropyl alcohol Total amount is 100% Viscosity 7.9 mPa ⁇ s * Reaction condensate of tetraethoxysilane and ethylene glycol (2-4 silicon atoms)
  • the coating composition of the present invention described above can be prepared, for example, by stirring and mixing each component.
  • the thus obtained paint of the present invention can be given a satin color tone by immersing the member to be treated and subjecting it to a surface treatment.
  • the member to be treated that can be surface-treated with the paint of the present invention is not particularly limited, and examples thereof include metal materials and resin materials.
  • the metal material include magnesium or a magnesium alloy, zinc or a zinc alloy, one type of metal selected from the group consisting of iron, copper, nickel, cobalt, chromium and tin, or an alloy containing two or more types of the above metals. It is done.
  • the resin material include one kind of synthetic resin selected from the group consisting of acrylonitrile / butadiene / styrene copolymer, polycarbonate, bismaleimide triazine, and polyimide, or a synthetic resin alloy composed of two or more kinds of the resins.
  • the shape of the member to be treated is not particularly limited as long as the paint of the present invention can contact the desired surface of the member to be treated by dipping.
  • the method for immersing the member to be treated in the paint of the present invention is not particularly limited, and the member to be treated may be simply immersed in the same manner as the coating using the coating material for normal immersion. It is preferable to use a dip-spin method because it is suitable for mass processing using a net cage such as an automobile part.
  • the conditions for immersion are not particularly limited. For example, the immersion may be performed once or more for several seconds to several minutes so that the paint of the present invention is sufficiently applied to the desired surface of the member to be processed.
  • the paint of the present invention contains aluminum which is base in potential, it is sacrificed especially when the surface of the member to be treated is zinc, or a zinc alloy such as zinc-iron, zinc-nickel or zinc-cobalt. Anticorrosion can be expected, and a coating film having sufficient corrosion resistance can be obtained even if the number of immersions is one.
  • the firing conditions are not particularly limited, and are, for example, about 1 to 60 minutes at 50 to 200 ° C. in the air.
  • the paint of the present invention may be further laminated by surface treatment, baking, etc. with the paint of the present invention.
  • a member to be treated (hereinafter referred to as “surface-treated product”) surface-treated with the paint of the present invention is given a satin color tone.
  • the satin tone means, for example, that the surface of the surface-treated product whose member to be treated is ABS has a metallic color, and the L value is 50.0 to 150.0, preferably 70 to 140.0. Means things. The L value was measured under the condition of Color45as15 using a colorimeter such as x-rite MA-94.
  • the film thickness of the paint of the present invention in the surface-treated product is not particularly limited, but as described above, the paint of the present invention can uniformly impart a satin tone even when immersed once, and provides a sufficiently corrosion-resistant film.
  • it may be about 0.1 to 10 ⁇ m.
  • the surface-treated product has high corrosion resistance.
  • red rust is generated in 740 hours.
  • the surface treatment product is further subjected to the surface treatment with the paint of the present invention. In the salt spray test, red rust is not generated for 2000 hours or more.
  • the above-mentioned surface-treated product is preferably used for parts such as two-wheeled vehicles and automobiles configured by galvanization.
  • alkoxysilane oligomer was prepared in the same manner as in Example 1 described in WO2014 / 207855. That is, aluminum chloride hexahydrate (1.8 g) was added to ethylene glycol (336 g), and this was heated to 50 ° C. with a mantle heater while stirring, and tetraethoxysilane (564 g) was mixed. Then, the alcohol produced during the substitution reaction was subjected to a condensation reaction for 2 hours without fractional distillation to obtain an alkoxysilane oligomer. The reaction rate of tetraethoxysilane was 100%.
  • the obtained alkoxysilane oligomer was a reaction condensate of tetraethoxysilane and ethylene glycol, and the number of silicon atoms in the oligomer was 2 to 4.
  • the obtained alkoxysilane oligomer was a reaction condensate of tetraethoxysilane and triethylene glycol, and the number of silicon atoms in the oligomer was 2 to 4.
  • the obtained alkoxysilane oligomer was a reaction condensate of tetraethoxysilane and 1,3-butylene glycol, and the number of silicon atoms in the oligomer was 2 to 4.
  • the obtained alkoxysilane oligomer is a reaction condensate of tetraethoxysilane and water, and gelled after 3 days of preparation, so that the number of silicon atoms in this oligomer is considered to be 5 or more.
  • Example 1 Preparation of dipping satin paint (stainless steel): Aluminum flakes (VP / 11329: manufactured by Toyo Aluminum Co., Ltd .: average piece thickness 30 nm, average particle diameter 13 ⁇ m) as metallic aluminum 1%, acrylic resin (H # 26-78: manufactured by Toei Kasei Co., Ltd.) 20%, 3% of alkoxysilane oligomer prepared in Production Example 1, 30% of 1-methoxy-2-propanol, and isopropyl alcohol in a total amount of 100%. Color) was obtained (viscosity was 7.4 mPa ⁇ s). This paint had a slow precipitation rate of aluminum flakes and was stable for more than half a year at room temperature.
  • Example 2 Preparation of dipping satin paint (stainless steel): Aluminum flakes (VP / 11329: manufactured by Toyo Aluminum Co., Ltd .: average piece thickness 30 nm, average particle diameter 13 ⁇ m) as metallic aluminum 1%, acrylic resin (H # 26-78: manufactured by Toei Kasei Co., Ltd.) 20%, 3% of the alkoxysilane oligomer prepared in Production Example 2, 30% of 1-methoxy-2-propanol, and isopropyl alcohol in a total amount of 100%. Color) was obtained (viscosity was 7.6 mPa ⁇ s). This paint had a slow precipitation rate of aluminum flakes and was stable for more than half a year at room temperature.
  • Example 3 Preparation of dipping satin paint (stainless steel): Aluminum flakes (VP / 11329: manufactured by Toyo Aluminum Co., Ltd .: average piece thickness 30 nm, average particle diameter 13 ⁇ m) as metallic aluminum 1%, acrylic resin (H # 26-78: manufactured by Toei Kasei Co., Ltd.) 20%, 3% of alkoxysilane oligomer prepared in Production Example 3, 30% of 1-methoxy-2-propanol, and isopropyl alcohol in a total amount of 100%. Color) was obtained (viscosity was 7.5 mPa ⁇ s). This paint had a slow precipitation rate of aluminum flakes and was stable for more than half a year at room temperature.
  • Example 4 Preparation of dipping satin paint (stainless steel): Aluminum flakes (VP / 11329: manufactured by Toyo Aluminum Co., Ltd .: average piece thickness 30 nm, average particle diameter 13 ⁇ m) as metal aluminum 1%, phenol resin (JN COAT VW: JCU Co., Ltd.) and 20%, Stir and mix dipping satin paint (stainless steel) by stirring and mixing 3% of the alkoxysilane oligomer prepared in Production Example 1, 30% of 1-methoxy-2-propanol, and 100% of the total amount of isopropyl alcohol. Obtained (viscosity is 7.0 mPa ⁇ s). This paint had a slow precipitation rate of aluminum flakes and was stable for more than half a year at room temperature.
  • Example 5 Preparation of dipping satin paint (titanium): Aluminum flakes (5004/10: manufactured by Toyo Aluminum Co., Ltd .: average piece thickness 9 nm, average particle diameter 12 ⁇ m) as metal aluminum 1%, acrylic resin (H # 26-78: manufactured by Toei Kasei Co., Ltd.) 20%, 3% of alkoxysilane oligomer prepared in Production Example 1, 30% of 1-methoxy-2-propanol, and isopropyl alcohol in a total amount of 100%. Color) was obtained (viscosity was 7.9 mPa ⁇ s). This paint had a slow precipitation rate of aluminum flakes and was stable for more than half a year at room temperature.
  • Example 6 Preparation of dipping satin paint (stainless steel): Aluminum flakes (VP / 11329: manufactured by Toyo Aluminum Co., Ltd .: average piece thickness 30 nm, average particle diameter 13 ⁇ m) as metallic aluminum 1%, acrylic resin (H # 26-78: manufactured by Toei Kasei Co., Ltd.) 20%, 3% of alkoxysilane oligomer prepared in Production Example 4, 30% of 1-methoxy-2-propanol, and isopropyl alcohol in a total amount of 100%. Color) was obtained (7.3 mPa ⁇ s). This paint had a slow precipitation rate of aluminum flakes and gelled in 3 days at room temperature.
  • Example 7 Satin paint An ABS resin plate that has been sufficiently degreased is applied to the dipping satin paint (stainless steel color) prepared in Example 1 or the dipping satin paint (titanium color) prepared in Example 5 for 30 seconds. It was immersed to a certain extent and pulled up. Then, this was dried at room temperature and further baked at 70 ° C. for 20 minutes (film thickness is about 1 ⁇ m).
  • FIG. 1 shows the ABS resin before dipping the paint and the ABS resin after dipping the paint.
  • Example 8 Satin paint Put 10 M8-25 hexagon bolts (the surface is galvanized with chemical conversion treatment) into a mesh basket and immerse the satin paint for immersion (stainless steel color) prepared in Example 1 or the satin paint for immersion prepared in Example 5. It was immersed in (titanium color) for about 30 seconds and pulled up. Subsequently, the bolts with the mesh cage were dried at 400 rpm with a centrifugal dryer, and further baked at 180 ° C. for 20 minutes, so that the bolts were subjected to a surface treatment (the film thickness was about 1 ⁇ m). The external appearance of the bolt before the paint immersion and the bolt after the paint immersion is shown in FIG.
  • the bolts treated with any paint had a uniform appearance and a satin-like anodized color.
  • Test example 1 Salt spray test: The bolts surface-treated with the satin paint obtained in Example 8 were each subjected to a salt spray test in accordance with JIS Z 2371. For comparison, a salt spray test was also performed on untreated bolts. The results are shown in Table 1.
  • Example 9 Satin paint When a satin-like coating was applied to the magnesium test piece in the same manner as in Example 7, a satin-like alumite color was imparted with a uniform appearance.
  • Example 10 Satin paint When a satin-like coating was applied to the copper test piece in the same manner as in Example 7, a satin-like alumite color was imparted with a uniform appearance.
  • the satin-like paint for dipping of the present invention can provide corrosion resistance even with a thinner film thickness than before, and is sufficient to be dipped once. Therefore, it is suitable for processing a large amount of automobile parts and the like. more than

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  • Engineering & Computer Science (AREA)
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  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
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Abstract

The purpose of the present invention is to provide surface treatment technology with which protection of a raw material without damaging the raw material is possible with a simple process and which is capable of forming a metal appearance with high corrosion resistance and a controlled sheen. Said technology is: a satin finish immersion coating characterized in containing metal flakes with a mean particle diameter of 1-50 µm and a mean flake thickness of 5-50 nm, a silicon oligomer, and a resin; and a surface treatment method characterized in that a member to be treated is immersed in said satin finish immersion coating.

Description

浸漬用サテン調塗料およびこれを用いた表面処理方法Satin-like paint for dipping and surface treatment method using the same
　本発明は、浸漬用サテン調塗料およびこれを用いた表面処理方法に関する。 The present invention relates to a satin paint for dipping and a surface treatment method using the same.
　これまで、金属色ならびに金属光沢を得るためにめっきによる表面処理が行なわれてきた。めっきには、金属光沢を得ることに加え、素材金属の保護する目的も存在する。 So far, surface treatment by plating has been performed to obtain a metallic color and metallic luster. In addition to obtaining a metallic luster, the plating also has the purpose of protecting the material metal.
　しかしながら、市場は、装飾性や高級感を求める傾向にあり、めっきにより得られる金属光沢は光沢があり過ぎるため、装飾性や高級感に劣るとの指摘が多くあり、めっきの光沢性を制御してサテン調の色調とすることが求められていた。 However, the market has a tendency to demand decorativeness and luxury, and the metallic luster obtained by plating is too glossy, and there are many indications that it is inferior to decorativeness and luxury. Therefore, it was required to have a satin color tone.
　めっきでサテン調の色調を得るために、例えば、めっき液に添加される光沢剤の種類の変更や、粒径の小さい微粒子を添加しためっき液を用いる複合めっき、エマルションを添加しためっき液を用いるサテンめっき等の技術が知られている。 In order to obtain a satin color tone by plating, for example, a change in the type of brightener added to the plating solution, a composite plating using a plating solution to which fine particles having a small particle diameter are added, or a plating solution to which an emulsion is added is used. Techniques such as satin plating are known.
　しかしながら、これらの技術はいずれもめっきで行うため、全面に均一な光沢性を制御した金属外観を得ることは難しかった。 However, since all of these techniques are performed by plating, it is difficult to obtain a metal appearance with uniform gloss control over the entire surface.
　また、別の技術として、めっき等で得られた金属表面に、更に、ブラスト、陽極酸化等でサテン調の色調を得る技術もあるが、素材金属自体を傷めることとなり、素材を保護することはできない。 In addition, as another technology, there is also a technology to obtain a satin color tone by blasting, anodizing, etc. on the metal surface obtained by plating etc., but it will damage the material metal itself and protect the material Can not.
　更に、別の技術として、素材金属上に亜鉛フレークとバインダーにより組み立てられたコーティングを塗装してサテン調の色調を得る技術もあるが、液の安定性の問題から常時攪拌が必要であったり、粘度が高いため締結部材に用いた際に螺子部が詰まってしまう等の問題が言われている。（特許文献１）。 Furthermore, as another technology, there is also a technology to obtain a satin color tone by painting a coating assembled with zinc flakes and a binder on the raw metal, but constantly stirring is necessary due to the problem of liquid stability, There is a problem that the screw portion is clogged when used for a fastening member because of its high viscosity. (Patent Document 1).
特開平８－７３７７８号公報JP-A-8-73778
　従って、本発明の課題は、簡単な工程で、素材を傷めず、素材保護が可能であり、且つ高い耐食性を有し、光沢を制御したサテン調の色調を付与できる表面処理技術が求められており、この手段を提供することである。 Therefore, the object of the present invention is to provide a surface treatment technology that can protect a material without damaging the material, has a high corrosion resistance, and can provide a satin-like color tone with controlled gloss by a simple process. And providing this means.
　本発明者らは、上記課題を解決するために鋭意研究した結果、特定の大きさを有する金属薄片とシリコンオリゴマー等を組み合わせて塗料とすることにより、塗料中に前記金属薄片が分散し、沈殿することがないため、単なる浸漬により被処理物にサテン調の色調を付与できることを見出し、本発明を完成させた。 As a result of diligent research to solve the above problems, the inventors of the present invention combined a metal flake having a specific size with a silicon oligomer to form a paint, whereby the metal flake was dispersed in the paint and precipitated. Therefore, the present inventors have found that a satin-like color tone can be imparted to an object to be treated by simple dipping, and the present invention has been completed.
　すなわち、本発明は、平均粒子径が１～５０μｍであり、平均片厚が５～５０ｎｍである金属粉末、シリコンオリゴマー、樹脂を含有することを特徴とする浸漬用サテン調塗料である。 That is, the present invention is a satin-like paint for immersion characterized by containing metal powder, silicon oligomer, and resin having an average particle diameter of 1 to 50 μm and an average piece thickness of 5 to 50 nm.
　また、本発明は、被処理物を、上記浸漬用サテン調塗料に浸漬することを特徴とする表面処理方法である。 Further, the present invention is a surface treatment method characterized by immersing an object to be treated in the above-mentioned dipping satin paint.
　更に、本発明は、被処理物を、上記浸漬用サテン調塗料に浸漬して得られることを特徴とする表面処理製品である。 Furthermore, the present invention is a surface-treated product obtained by immersing an object to be treated in the above-mentioned dipping satin paint.
　本発明の浸漬用サテン調塗料は、これに含まれる金属薄片が分散し、沈殿することがないため、塗料の撹拌が不要であり、浸漬により被処理物にサテン調の色調を一様に付与できる The satin-like paint for immersion of the present invention does not require dispersion of the metal flakes contained therein and does not precipitate, so that stirring of the paint is unnecessary, and a satin-like color tone is uniformly imparted to the object to be treated by immersion. it can
　また、本発明の浸漬用サテン調塗料は、従来よりも薄い膜厚でも耐食性が得られ、しかも、浸漬する回数も一回で充分である。そのため、自動車等の部品のような大量の処理に用いるのに好適である。 In addition, the satin-like paint for dipping of the present invention can provide corrosion resistance even with a thinner film thickness than the conventional one, and the number of times of dipping is sufficient. Therefore, it is suitable for use in a large amount of processing such as parts for automobiles.
実施例７において得られた本発明の浸漬用サテン調塗料で表面を処理したＡＢＳ樹脂板の外観を示す図である（Ａ：塗装前、Ｂ：塗装後（ステンレス色）、Ｃ：塗装後（チタン色））It is a figure which shows the external appearance of the ABS resin board which processed the surface with the satin-tone paint for immersion of this invention obtained in Example 7 (A: Before painting, B: After painting (stainless steel color), C: After painting ( Titanium color)) 実施例８において得られた本発明の浸漬用サテン調塗料で表面を処理したボルトの外観を示す図である（Ａ：塗装前、Ｂ：塗装後（ステンレス色）、Ｃ：塗装後（チタン色））。It is a figure which shows the external appearance of the volt | bolt which processed the surface with the satin-tone paint for immersion of the present invention obtained in Example 8 (A: before painting, B: after painting (stainless steel color), C: after painting (titanium color) )).
　本発明の浸漬用サテン調塗料（以下、「本発明塗料」という）に用いられる金属薄片は平均粒子径が１～５０μｍ、好ましくは１～１０μｍであり、平均片厚が５～５０ｎｍ、好ましくは１～２５ｎｍである。金属の種類は、特に限定されず、例えば、亜鉛、鉄、ニッケル、銅、アルミニウム等が挙げられるが、これらの中でもアルミニウムが最も良くサテン調の色調を付与できるため好ましい。これら金属薄片は１種または２種以上を組み合わせて用いることもできる。また、このような金属薄片としては、例えば、常法に従って蒸着法等で得られるものや、市販品を利用することができる。このような金属薄片の市販品としては、例えば、ＰＳＬＥＮＤＡＬシリーズ（ＤＩＣ社）、Ｄｅｃｏｍｅｔシリーズ（東洋アルミ社）等を挙げることができる。なお、上記平均粒子径は光学顕微鏡で測定された５～２０程度の薄片の粒子径（長辺）の平均値であり、平均片厚はＳＥＭ象で観察された５～２０程度の薄片の膜厚の平均値である。 The metal flakes used in the satin paint for immersion of the present invention (hereinafter referred to as “the present paint”) have an average particle diameter of 1 to 50 μm, preferably 1 to 10 μm, and an average flake thickness of 5 to 50 nm, preferably 1 to 25 nm. The kind of metal is not particularly limited, and examples thereof include zinc, iron, nickel, copper, and aluminum. Among these, aluminum is the best because it can give a satin color tone. These metal flakes can be used alone or in combination of two or more. Moreover, as such a metal flake, what is obtained by a vapor deposition method etc. according to a conventional method, for example, and a commercial item can be utilized. Examples of such commercially available metal flakes include PSLENDAL series (DIC Corporation) and Decomet series (Toyo Aluminum Corporation). The average particle diameter is an average value of the particle diameter (long side) of a thin piece of about 5 to 20 measured by an optical microscope, and the average piece thickness is a film of a thin piece of about 5 to 20 observed in an SEM image. Average thickness.
　なお、本発明塗料における上記金属薄片の含有量は特に限定されず、例えば、０.１～１０質量％（以下、単に「％」という）、好ましくは０.３～１.０％である。 The content of the metal flakes in the paint of the present invention is not particularly limited, and is, for example, 0.1 to 10% by mass (hereinafter simply referred to as “%”), preferably 0.3 to 1.0%.
　本発明塗料に用いられるシリコンオリゴマーは、特に限定されず、例えば、アルコキシシランオリゴマー等が挙げられる。このアルコキシシランオリゴマーは、アルコキシシランと水や多価アルコールとの反応縮合物であり、これはアルコキシシランのアルコキシ基と、水や多価アルコールのヒドロキシ基が縮合したものである。なお、アルコキシシランオリゴマー中のシリコン原子数は特に限定されないが、例えば、２～８のもの、より好ましくは２～４のものである。 The silicon oligomer used in the paint of the present invention is not particularly limited, and examples thereof include alkoxysilane oligomers. This alkoxysilane oligomer is a reaction condensate of alkoxysilane and water or polyhydric alcohol, which is a condensate of the alkoxy group of alkoxysilane and the hydroxy group of water or polyhydric alcohol. The number of silicon atoms in the alkoxysilane oligomer is not particularly limited, but is 2 to 8, for example, more preferably 2 to 4.
　上記アルコキシシランオリゴマーの原料となるアルコキシシランとしては、特に限定されないが、例えば、テトラエトキシシラン、テトラメトキシシラン等が挙げられる。 The alkoxysilane used as the raw material for the alkoxysilane oligomer is not particularly limited, and examples thereof include tetraethoxysilane and tetramethoxysilane.
　また、上記アルコキシシランオリゴマーの原料となる多価アルコールとしては、特に限定されないが、例えば、エチレングリコール、ジエチレングリコール、トリエチレングリコール、１，３－ブチレングリコール等が挙げられる。 The polyhydric alcohol used as the raw material for the alkoxysilane oligomer is not particularly limited, and examples thereof include ethylene glycol, diethylene glycol, triethylene glycol, and 1,3-butylene glycol.
　これらアルコキシシランオリゴマーは、アルコキシシランと水や多価アルコールとを、触媒としての金属塩の存在下で５０℃程度で２時間程度縮合反応させ、反応の際に生成するアルコールを分留しないことにより得られる。 These alkoxysilane oligomers are obtained by subjecting alkoxysilane and water or a polyhydric alcohol to a condensation reaction at about 50 ° C. for about 2 hours in the presence of a metal salt as a catalyst, and by not fractionating the alcohol produced during the reaction. can get.
　上記縮合反応において、触媒として使用される金属塩としては、特に限定されないが、例えば、塩化アルミニウム、塩化亜鉛、塩化鉄等が挙げられる。 In the above condensation reaction, the metal salt used as a catalyst is not particularly limited, and examples thereof include aluminum chloride, zinc chloride, and iron chloride.
　上記したアルコキシシランと水や多価アルコールとの反応縮合物の中でも、アルコキシシランと多価アルコールとの反応縮合物が好ましく、アルコキシシランと、エチレングリコール、ジエチレングリコール、トリエチレングリコール、１，３－ブチレングリコール等の２価アルコールとの反応縮合物が、これを本発明塗料とした際の安定性の点から特に好ましい。 Among the above reaction condensates of alkoxysilane and water or polyhydric alcohol, the reaction condensate of alkoxysilane and polyhydric alcohol is preferable, and alkoxysilane, ethylene glycol, diethylene glycol, triethylene glycol, 1,3-butylene. A reaction condensate with a dihydric alcohol such as glycol is particularly preferred from the viewpoint of stability when it is used as the coating material of the present invention.
　このようなアルコキシシランとエチレングリコール、ジエチレングリコール、トリエチレングリコール、１，３－ブチレングリコール等の２価アルコールとの反応縮合物としては、国際公開パンフレットＷＯ２０１４／２０７８８５に記載のものが好ましく、特にこのパンフレットの実施例に記載されているものが好ましい。 As such a reaction condensate of alkoxysilane and a dihydric alcohol such as ethylene glycol, diethylene glycol, triethylene glycol, 1,3-butylene glycol and the like, those described in International Publication Pamphlet WO2014 / 20785 are preferable, and this pamphlet is particularly preferable. Those described in the examples are preferred.
　これらのシリコンオリゴマーは１種または２種以上を組み合わせて用いることもできる。 These silicon oligomers can be used alone or in combination of two or more.
　また、本発明塗料における上記シリコンオリゴマーの含有量は特に限定されず、例えば、０.１％以上であり、好ましくは０.５～５.０％である。 Further, the content of the silicon oligomer in the paint of the present invention is not particularly limited, and is, for example, 0.1% or more, preferably 0.5 to 5.0%.
　本発明塗料に用いられる樹脂は、特に限定されず、例えば、アクリル樹脂、ウレタン樹脂、フェノール樹脂、エポキシ樹脂等が挙げられる。これらの樹脂の中でもアクリル樹脂が好ましく、アクリル樹脂の中でもメタアクリル酸アルキルエステル共重合体、コロイダルシリカ・アクリル複合体、エチレン・アクリル酸共重合物アンモニウム塩がより好ましく、メタアクリル酸アルキルエステル共重合体が特に好ましい。これら樹脂は１種または２種以上を組み合わせて用いることもできる。 The resin used for the paint of the present invention is not particularly limited, and examples thereof include acrylic resins, urethane resins, phenol resins, epoxy resins and the like. Among these resins, acrylic resins are preferable. Among acrylic resins, methacrylic acid alkyl ester copolymers, colloidal silica / acrylic composites, and ethylene / acrylic acid copolymer ammonium salts are more preferable. Coalescence is particularly preferred. These resins may be used alone or in combination of two or more.
　なお、本発明塗料における上記樹脂の含有量は特に限定されず、例えば、０.１～５０％、好ましくは１～２０％である。 The content of the resin in the paint of the present invention is not particularly limited, and is, for example, 0.1 to 50%, preferably 1 to 20%.
　本発明塗料には、更に、顔料を含有させることができる。本発明塗料に用いられる顔料は、上記金属薄片に該当するものを除く以外は特に限定されず、例えば、アルミニウム、チタン、ケイ素、バリウム、ジルコニウム等金属の酸化物、硫酸塩またはそれらによる処理物等の金属由来の顔料、ポリエチレン、ポリプロピレン等のポリオレフィン系樹脂、ポリテトラフルオロエチレン、テトラフルオロエチレン－パーフルオロアルキルビニルエーテル共重合体等のフッ素系樹脂等の樹脂由来の顔料、カーボンブラック等が挙げられる。これらの顔料の中でもカーボンブラックが好ましい。これら顔料は１種または２種以上を組み合わせて用いることもできる。 The pigment of the present invention can further contain a pigment. The pigment used in the paint of the present invention is not particularly limited except that it does not correspond to the above-mentioned metal flakes. For example, aluminum, titanium, silicon, barium, zirconium and other metal oxides, sulfates or treated products thereof, etc. Examples thereof include pigments derived from these metals, polyolefin resins such as polyethylene and polypropylene, pigments derived from resins such as fluororesins such as polytetrafluoroethylene and tetrafluoroethylene-perfluoroalkyl vinyl ether copolymers, and carbon black. Among these pigments, carbon black is preferable. These pigments can be used alone or in combination of two or more.
　なお、本発明塗料における上記顔料の含有量は特に限定されず、例えば、１０％未満であり、好ましくは０.３～１.０％である。 The content of the pigment in the paint of the present invention is not particularly limited, and is, for example, less than 10%, preferably 0.3 to 1.0%.
　また、本発明塗料には、本発明の効果を損なわない範囲で、摩擦係数調整剤、増膜剤等を含有させてもよい。摩擦係数調整剤は、特に限定されず、例えばポリエチレンワックス等が挙げられる。増膜剤は、特に限定されず、例えば、ヒュームドシリカ等が挙げられる。 In addition, the paint of the present invention may contain a friction coefficient adjusting agent, a film thickener and the like as long as the effects of the present invention are not impaired. The friction coefficient adjusting agent is not particularly limited, and examples thereof include polyethylene wax. The film thickener is not particularly limited, and examples thereof include fumed silica.
　更に、本発明塗料は、例えば、１－メトキシ２－プロパノール等の高沸点溶媒、イソプロピルアルコール等で適宜希釈して粘度を調整してもよい。本発明塗料の粘度は特に限定されないが、例えば、５～１５ｍＰａ・ｓ、好ましくは７～１０ｍＰａ・ｓである。 Furthermore, the viscosity of the paint of the present invention may be adjusted by appropriately diluting with a high boiling point solvent such as 1-methoxy-2-propanol, isopropyl alcohol or the like. The viscosity of the paint of the present invention is not particularly limited, but is, for example, 5 to 15 mPa · s, preferably 7 to 10 mPa · s.
　本発明塗料の好ましい態様としては、例えば以下のものが挙げられる。 Favorable embodiments of the paint of the present invention include the following, for example.
＜ステンレス色＞
　アルミニウム薄片（平均粒子径１０～１５μｍ、平均片厚２０～５０ｎｍ
　）　　　　　　　　　　　　　　　　　　　　　０.３～１０％
　アクリル酸エステル共重合体　　　　　　　　　１～５０％
　アルコキシシランオリゴマー　　　　　　　　　０.５～５.０％
　イソプロピルアルコール　　　　　　　　　　　総量が１００％となる量
　粘度　　　　　　　　　　　　　　　　　　　　７.４　ｍＰａ・ｓ
※テトラエトキシシランとエチレングリコールの反応縮合物（シリコン原子の数は２～４） <Stainless steel color>
Aluminum flakes (average particle size 10-15μm, average piece thickness 20-50nm
) 0.3-10%
Acrylic ester copolymer 1-50%
Alkoxysilane oligomer 0.5-5.0%
Isopropyl alcohol Total amount to be 100% Viscosity 7.4 mPa · s
* Reaction condensate of tetraethoxysilane and ethylene glycol (2-4 silicon atoms)
＜チタン色＞
　アルミニウム薄片（平均粒子径１０～１５μｍ、平均片厚５～１５ｎｍ）　　　　　　　　　　　　　　　　　　　　　　０.３～１０％
　アクリル酸エステル共重合体　　　　　　　　１～５０％
　アルコキシシランオリゴマー※　　　　　　　 ０.５～５.０％
　イソプロピルアルコール　　　　　　　　　　総量が１００％となる量
　粘度　　　　　　　　　　　　　　　　　　　７.９　ｍＰａ・ｓ
※テトラエトキシシランとエチレングリコールの反応縮合物（シリコン原子の数は２～４） <Titanium color>
Aluminum flakes (average particle size 10-15 μm, average piece thickness 5-15 nm) 0.3-10%
Acrylic ester copolymer 1-50%
Alkoxysilane oligomer * 0.5-5.0%
Isopropyl alcohol Total amount is 100% Viscosity 7.9 mPa · s
* Reaction condensate of tetraethoxysilane and ethylene glycol (2-4 silicon atoms)
　以上説明した本発明塗料は、例えば、各成分を撹拌、混合することにより調製することができる。 The coating composition of the present invention described above can be prepared, for example, by stirring and mixing each component.
　斯くして得られる本発明塗料に、被処理部材を浸漬して表面処理することによりサテン調の色調を付与することができる。 The thus obtained paint of the present invention can be given a satin color tone by immersing the member to be treated and subjecting it to a surface treatment.
　本発明塗料で表面処理することのできる被処理部材としては、特に限定されず、例えば、金属材、樹脂材等が挙げられる。金属材としては、マグネシウムまたはマグネシウム合金、亜鉛または亜鉛合金や、鉄、銅、ニッケル、コバルト、クロムおよびスズからなる群から選ばれる金属の１種または前記金属の２種以上を含む合金等が挙げられる。樹脂材としては、アクリロニトリル・ブタジエン・スチレン共重合体、ポリカーボネート、ビスマレイミドトリアジンおよびポリイミドからなる群から選ばれる合成樹脂の１種または前記樹脂の２種以上からなる合成樹脂アロイ等が挙げられる。また、被処理部材の形状は、浸漬により被処理部材の所望の表面に本発明塗料が接触できるような形状であれば特に限定されない。 The member to be treated that can be surface-treated with the paint of the present invention is not particularly limited, and examples thereof include metal materials and resin materials. Examples of the metal material include magnesium or a magnesium alloy, zinc or a zinc alloy, one type of metal selected from the group consisting of iron, copper, nickel, cobalt, chromium and tin, or an alloy containing two or more types of the above metals. It is done. Examples of the resin material include one kind of synthetic resin selected from the group consisting of acrylonitrile / butadiene / styrene copolymer, polycarbonate, bismaleimide triazine, and polyimide, or a synthetic resin alloy composed of two or more kinds of the resins. The shape of the member to be treated is not particularly limited as long as the paint of the present invention can contact the desired surface of the member to be treated by dipping.
　上記被処理部材を本発明塗料に浸漬する方法は、特に限定されず、通常浸漬用の塗料を用いた塗装と同様に単に被処理部材を浸漬するだけでもよいが、本発明塗料は特にボルトナット等の自動車部品のような網かごを用いた大量処理に向いているためディップ－スピン（Ｄｉｐ－Ｓｐｉｎ）法を用いることが好ましい。また、浸漬の条件は特に限定されず、例えば、被処理部材の所望の表面に本発明塗料が十分つきまわるように数秒～数分程度、１回以上浸漬すればよい。 The method for immersing the member to be treated in the paint of the present invention is not particularly limited, and the member to be treated may be simply immersed in the same manner as the coating using the coating material for normal immersion. It is preferable to use a dip-spin method because it is suitable for mass processing using a net cage such as an automobile part. The conditions for immersion are not particularly limited. For example, the immersion may be performed once or more for several seconds to several minutes so that the paint of the present invention is sufficiently applied to the desired surface of the member to be processed.
　なお、本発明塗料は、電位的に卑であるアルミニウムを含んでいるため、特に被処理部材の表面が亜鉛や、亜鉛－鉄、亜鉛－ニッケル、亜鉛－コバルト等の亜鉛合金である場合、犠牲防食が期待でき、浸漬回数が１回でも十分に耐食性のある塗膜が得られる。 Since the paint of the present invention contains aluminum which is base in potential, it is sacrificed especially when the surface of the member to be treated is zinc, or a zinc alloy such as zinc-iron, zinc-nickel or zinc-cobalt. Anticorrosion can be expected, and a coating film having sufficient corrosion resistance can be obtained even if the number of immersions is one.
　浸漬後は、更に焼成を行ってもよい。焼成の条件は特に限定されず、例えば、大気中、５０～２００℃で１～６０分程度である。 After the immersion, further baking may be performed. The firing conditions are not particularly limited, and are, for example, about 1 to 60 minutes at 50 to 200 ° C. in the air.
　本発明塗料で被処理部材を表面処理した後は、更に本発明塗料で表面処理、焼成等して本発明塗料を積層してもよい。 After the surface of the member to be treated is treated with the paint of the present invention, the paint of the present invention may be further laminated by surface treatment, baking, etc. with the paint of the present invention.
　斯くして本発明塗料で表面処理された被処理部材（以下、「表面処理製品」という）は、サテン調の色調が付与される。ここでサテン調とは、例えば、被処理部材がＡＢＳである表面処理製品の表面が金属色を有していて、かつ、Ｌ値が５０.０～１５０.０、好ましくは７０～１４０.０のものをいう。なお、Ｌ値は、ｘ－ｒｉｔｅＭＡ－９４等の測色計を用い、Ｃｏｌｏｒ４５ａｓ１５の条件にて測定されたものである。 Thus, a member to be treated (hereinafter referred to as “surface-treated product”) surface-treated with the paint of the present invention is given a satin color tone. Here, the satin tone means, for example, that the surface of the surface-treated product whose member to be treated is ABS has a metallic color, and the L value is 50.0 to 150.0, preferably 70 to 140.0. Means things. The L value was measured under the condition of Color45as15 using a colorimeter such as x-rite MA-94.
　また、表面処理製品における本発明塗料の膜厚は特に限定されないが、上記したように本発明塗料は浸漬が１回でもサテン調の色調を一様に付与でき、十分に耐食性のある膜を付与することができるため、例えば、０.１～１０μｍ程度でよい。 The film thickness of the paint of the present invention in the surface-treated product is not particularly limited, but as described above, the paint of the present invention can uniformly impart a satin tone even when immersed once, and provides a sufficiently corrosion-resistant film. For example, it may be about 0.1 to 10 μm.
　更に、表面処理製品は、耐食性が高く、例えば、亜鉛めっきに化成処理のみを行った場合には、７４０時間にて、赤錆が発生するが、例えば、これに更に本発明塗料で表面処理をすれば塩水噴霧試験にて２０００時間以上、赤錆が発生しなくなる。 Furthermore, the surface-treated product has high corrosion resistance. For example, when only the chemical conversion treatment is applied to galvanization, red rust is generated in 740 hours. For example, the surface treatment product is further subjected to the surface treatment with the paint of the present invention. In the salt spray test, red rust is not generated for 2000 hours or more.
　上記表面処理製品は、亜鉛めっきにより構成されている二輪車、自動車等の部品に利用することが好適である。 The above-mentioned surface-treated product is preferably used for parts such as two-wheeled vehicles and automobiles configured by galvanization.
　以下、本発明を実施例等を挙げて詳細に説明するが、本発明はこれら実施例等に何ら限定されるものではない。 Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.
製　造　例　１
　　　アルコキシシランオリゴマーの調製：
　ＷＯ２０１４／２０７８８５に記載の実施例１と同様にしてアルコキシシランオリゴマーを調製した。すなわち、エチレングリコール（３３６ｇ）に塩化アルミニウム・６水和物（１.８ｇ）を添加し、これを、撹拌しながらマントルヒーターで５０℃に加温したものに、テトラエトキシシラン（５６４ｇ）を混合し、置換反応時に生成するアルコールを分留せずに２時間縮合反応させてアルコキシシランオリゴマーを得た。なお、テトラエトキシシランの反応率は１００％であった。 Manufacturing example 1
Preparation of alkoxysilane oligomer:
An alkoxysilane oligomer was prepared in the same manner as in Example 1 described in WO2014 / 207855. That is, aluminum chloride hexahydrate (1.8 g) was added to ethylene glycol (336 g), and this was heated to 50 ° C. with a mantle heater while stirring, and tetraethoxysilane (564 g) was mixed. Then, the alcohol produced during the substitution reaction was subjected to a condensation reaction for 2 hours without fractional distillation to obtain an alkoxysilane oligomer. The reaction rate of tetraethoxysilane was 100%.
　得られたアルコキシシランオリゴマーは、テトラエトキシシランとエチレングリコールの反応縮合物であり、このオリゴマー中のシリコン原子の数は２～４であった。 The obtained alkoxysilane oligomer was a reaction condensate of tetraethoxysilane and ethylene glycol, and the number of silicon atoms in the oligomer was 2 to 4.
製　造　例　２
　　　アルコキシシランオリゴマーの調製：
　上記製造例１において、エチレングリコールをトリエチレングリコール８１０.９ｇ（５.４ｍｏｌ）とする以外はと同様にしてアルコキシシリコンオリゴマー（ＷＯ２０１４／２０７８８５に記載の実施例１２と同様のもの）を調製した。なお、テトラエトキシシランの反応率は１００％であった。 Manufacturing example 2
Preparation of alkoxysilane oligomer:
An alkoxysilicon oligomer (similar to Example 12 described in WO2014 / 207855) was prepared in the same manner as in Production Example 1 except that ethylene glycol was changed to 810.9 g (5.4 mol) of triethylene glycol. The reaction rate of tetraethoxysilane was 100%.
　得られたアルコキシシランオリゴマーは、テトラエトキシシランとトリエチレングリコールの反応縮合物であり、このオリゴマー中のシリコン原子の数は２～４であった。 The obtained alkoxysilane oligomer was a reaction condensate of tetraethoxysilane and triethylene glycol, and the number of silicon atoms in the oligomer was 2 to 4.
製　造　例　３　
　　　アルコキシシランオリゴマーの調製：
　上記製造例１において、エチレングリコールを１,３－ブチレングリコール４８６.６ｇ（５.４ｍｏｌ）とする以外は実施例１と同様にしてアルコキシシランオリゴマー（ＷＯ２０１４／２０７８８５に記載の実施例１３と同様のもの）を調製した。なお、テトラエトキシシランの反応率は１００％であった。 Manufacturing example 3
Preparation of alkoxysilane oligomer:
In the above Production Example 1, an alkoxysilane oligomer (similar to Example 13 described in WO2014 / 207855) was used in the same manner as in Example 1 except that ethylene glycol was changed to 486.6 g (5.4 mol) of 1,3-butylene glycol. Prepared). The reaction rate of tetraethoxysilane was 100%.
　得られたアルコキシシランオリゴマーは、テトラエトキシシランと１,３－ブチレングリコールの反応縮合物であり、このオリゴマー中のシリコン原子の数は２～４であった。 The obtained alkoxysilane oligomer was a reaction condensate of tetraethoxysilane and 1,3-butylene glycol, and the number of silicon atoms in the oligomer was 2 to 4.
製　造　例　４　
　　　アルコキシシランオリゴマーの調製：
　製造例１のエチレングリコールを水９７.２ｇ（５.４ｍｏｌ）とする以外は実施例１と同様にしてアルコキシシランオリゴマーを調製した。なお、テトラエトキシシランの反応率は１００％であった。 Manufacturing example 4
Preparation of alkoxysilane oligomer:
An alkoxysilane oligomer was prepared in the same manner as in Example 1 except that the ethylene glycol of Production Example 1 was changed to 97.2 g (5.4 mol) of water. The reaction rate of tetraethoxysilane was 100%.
　得られたアルコキシシランオリゴマーは、テトラエトキシシランと水の反応縮合物であり、放置により調製３日後にゲル化したことからこのオリゴマー中のシリコン原子の数は５以上であると考えられる。 The obtained alkoxysilane oligomer is a reaction condensate of tetraethoxysilane and water, and gelled after 3 days of preparation, so that the number of silicon atoms in this oligomer is considered to be 5 or more.
実　施　例　１
　　　浸漬用サテン調塗料（ステンレス色）の調製：
　アルミニウム薄片（ＶＰ／１１３２９：東洋アルミ（株）社製：平均片厚３０ｎｍ、平均粒子径１３μｍ）を金属アルミニウムとして１％、アクリル樹脂（Ｈ＃２６－７８：東栄化成（株）社製）を２０％、製造例１で調製したアルコキシシランオリゴマーを３％、１－メトキシ２－プロパノールを３０％と、イソプロピルアルコールを総量が１００％となる量で撹拌、混合して浸漬用サテン調塗料（ステンレス色）を得た（粘度は７.４ｍＰａ・ｓ）。なお、この塗料はアルミニウム薄片の沈殿速度が遅く、室温放置にて半年以上安定であった。 Example 1
Preparation of dipping satin paint (stainless steel):
Aluminum flakes (VP / 11329: manufactured by Toyo Aluminum Co., Ltd .: average piece thickness 30 nm, average particle diameter 13 μm) as metallic aluminum 1%, acrylic resin (H # 26-78: manufactured by Toei Kasei Co., Ltd.) 20%, 3% of alkoxysilane oligomer prepared in Production Example 1, 30% of 1-methoxy-2-propanol, and isopropyl alcohol in a total amount of 100%. Color) was obtained (viscosity was 7.4 mPa · s). This paint had a slow precipitation rate of aluminum flakes and was stable for more than half a year at room temperature.
実　施　例　２
　　　浸漬用サテン調塗料（ステンレス色）の調製：
　アルミニウム薄片（ＶＰ／１１３２９：東洋アルミ（株）社製：平均片厚３０ｎｍ、平均粒子径１３μｍ）を金属アルミニウムとして１％、アクリル樹脂（Ｈ＃２６－７８：東栄化成（株）社製）を２０％、製造例２で調製したアルコキシシランオリゴマーを３％、１－メトキシ２－プロパノールを３０％と、イソプロピルアルコールを総量が１００％となる量で撹拌、混合して浸漬用サテン調塗料（ステンレス色）を得た（粘度は７.６ｍＰａ・ｓ）。なお、この塗料はアルミニウム薄片の沈殿速度が遅く、室温放置にて半年以上安定であった。 Example 2
Preparation of dipping satin paint (stainless steel):
Aluminum flakes (VP / 11329: manufactured by Toyo Aluminum Co., Ltd .: average piece thickness 30 nm, average particle diameter 13 μm) as metallic aluminum 1%, acrylic resin (H # 26-78: manufactured by Toei Kasei Co., Ltd.) 20%, 3% of the alkoxysilane oligomer prepared in Production Example 2, 30% of 1-methoxy-2-propanol, and isopropyl alcohol in a total amount of 100%. Color) was obtained (viscosity was 7.6 mPa · s). This paint had a slow precipitation rate of aluminum flakes and was stable for more than half a year at room temperature.
実　施　例　３
　　　浸漬用サテン調塗料（ステンレス色）の調製：
　アルミニウム薄片（ＶＰ／１１３２９：東洋アルミ（株）社製：平均片厚３０ｎｍ、平均粒子径１３μｍ）を金属アルミニウムとして１％、アクリル樹脂（Ｈ＃２６－７８：東栄化成（株）社製）を２０％、製造例３で調製したアルコキシシランオリゴマーを３％、１－メトキシ２－プロパノールを３０％と、イソプロピルアルコールを総量が１００％となる量で撹拌、混合して浸漬用サテン調塗料（ステンレス色）を得た（粘度は７.５ｍＰａ・ｓ）。なお、この塗料はアルミニウム薄片の沈殿速度が遅く、室温放置にて半年以上安定であった。 Example 3
Preparation of dipping satin paint (stainless steel):
Aluminum flakes (VP / 11329: manufactured by Toyo Aluminum Co., Ltd .: average piece thickness 30 nm, average particle diameter 13 μm) as metallic aluminum 1%, acrylic resin (H # 26-78: manufactured by Toei Kasei Co., Ltd.) 20%, 3% of alkoxysilane oligomer prepared in Production Example 3, 30% of 1-methoxy-2-propanol, and isopropyl alcohol in a total amount of 100%. Color) was obtained (viscosity was 7.5 mPa · s). This paint had a slow precipitation rate of aluminum flakes and was stable for more than half a year at room temperature.
実　施　例　４
　　　浸漬用サテン調塗料（ステンレス色）の調製：
　アルミニウム薄片（ＶＰ／１１３２９：東洋アルミ（株）社製：平均片厚３０ｎｍ、平均粒子径１３μｍ）を金属アルミニウムとして１％、フェノール樹脂（ＪＮ　ＣＯＡＴ　ＶＷ：（株）ＪＣＵ社製）と２０％、製造例１で調製したアルコキシシランオリゴマーを３％、１－メトキシ２－プロパノールを３０％と、イソプロピルアルコールを総量が１００％となる量で撹拌、混合して浸漬用サテン調塗料（ステンレス色）を得た（粘度は７.０ｍＰａ・ｓ）。なお、この塗料はアルミニウム薄片の沈殿速度が遅く、室温放置にて半年以上安定であった。 Example 4
Preparation of dipping satin paint (stainless steel):
Aluminum flakes (VP / 11329: manufactured by Toyo Aluminum Co., Ltd .: average piece thickness 30 nm, average particle diameter 13 μm) as metal aluminum 1%, phenol resin (JN COAT VW: JCU Co., Ltd.) and 20%, Stir and mix dipping satin paint (stainless steel) by stirring and mixing 3% of the alkoxysilane oligomer prepared in Production Example 1, 30% of 1-methoxy-2-propanol, and 100% of the total amount of isopropyl alcohol. Obtained (viscosity is 7.0 mPa · s). This paint had a slow precipitation rate of aluminum flakes and was stable for more than half a year at room temperature.
実　施　例　５
　　　浸漬用サテン調塗料（チタン色）の調製：
　アルミニウム薄片（５００４／１０：東洋アルミ（株）社製：平均片厚９ｎｍ、平均粒子径１２μｍ）を金属アルミニウムとして１％、アクリル樹脂（Ｈ＃２６－７８：東栄化成（株）社製）を２０％、製造例１で調製したアルコキシシランオリゴマーを３％、１－メトキシ２－プロパノールを３０％と、イソプロピルアルコールを総量が１００％となる量で撹拌、混合して浸漬用サテン調塗料（チタン色）を得た（粘度は７.９ｍＰａ・ｓ）。なお、この塗料はアルミニウム薄片の沈殿速度が遅く、室温放置にて半年以上安定であった。 Example 5
Preparation of dipping satin paint (titanium):
Aluminum flakes (5004/10: manufactured by Toyo Aluminum Co., Ltd .: average piece thickness 9 nm, average particle diameter 12 μm) as metal aluminum 1%, acrylic resin (H # 26-78: manufactured by Toei Kasei Co., Ltd.) 20%, 3% of alkoxysilane oligomer prepared in Production Example 1, 30% of 1-methoxy-2-propanol, and isopropyl alcohol in a total amount of 100%. Color) was obtained (viscosity was 7.9 mPa · s). This paint had a slow precipitation rate of aluminum flakes and was stable for more than half a year at room temperature.
実　施　例　６
　　　浸漬用サテン調塗料（ステンレス色）の調製：
　アルミニウム薄片（ＶＰ／１１３２９：東洋アルミ（株）社製：平均片厚３０ｎｍ、平均粒子径１３μｍ）を金属アルミニウムとして１％、アクリル樹脂（Ｈ＃２６－７８：東栄化成（株）社製）を２０％、製造例４で調製したアルコキシシランオリゴマーを３％、１－メトキシ２－プロパノールを３０％と、イソプロピルアルコールを総量が１００％となる量で撹拌、混合して浸漬用サテン調塗料（ステンレス色）を得た（７.３ｍＰａ・ｓ）。　なお、この塗料はアルミニウム薄片の沈殿速度が遅く、室温放置にて３日でゲル化した。 Example 6
Preparation of dipping satin paint (stainless steel):
Aluminum flakes (VP / 11329: manufactured by Toyo Aluminum Co., Ltd .: average piece thickness 30 nm, average particle diameter 13 μm) as metallic aluminum 1%, acrylic resin (H # 26-78: manufactured by Toei Kasei Co., Ltd.) 20%, 3% of alkoxysilane oligomer prepared in Production Example 4, 30% of 1-methoxy-2-propanol, and isopropyl alcohol in a total amount of 100%. Color) was obtained (7.3 mPa · s). This paint had a slow precipitation rate of aluminum flakes and gelled in 3 days at room temperature.
実　施　例　７
　　　サテン調塗装：
　ＡＢＳ樹脂板に十分な脱脂処理を施したしたものを、実施例１で調製した浸漬用サテン調塗料（ステンレス色）または実施例５で調製した浸漬用サテン調塗料（チタン色）に、３０秒程度浸漬し、引き上げた。その後、これを室温で乾燥させ、更に７０℃で２０分間焼成した（膜厚は１μｍ程度）。塗料浸漬前のＡＢＳ樹脂と塗料浸漬後のＡＢＳ樹脂を図１に示した。 Example 7
Satin paint:
An ABS resin plate that has been sufficiently degreased is applied to the dipping satin paint (stainless steel color) prepared in Example 1 or the dipping satin paint (titanium color) prepared in Example 5 for 30 seconds. It was immersed to a certain extent and pulled up. Then, this was dried at room temperature and further baked at 70 ° C. for 20 minutes (film thickness is about 1 μm). FIG. 1 shows the ABS resin before dipping the paint and the ABS resin after dipping the paint.
　実施例１で調製した浸漬用サテン調塗料（ステンレス色）で処理した樹脂板の外観をＬ値で評価した結果１３４.６の値を示した。また、この樹脂板は、一様な外観でサテン調のアルマイト色が付与されていた。 As a result of evaluating the appearance of the resin plate treated with the dipping satin-tone paint (stainless steel color) prepared in Example 1, the value of 134.6 was shown. Further, this resin plate was given a satin-like alumite color with a uniform appearance.
　実施例５で調製した浸漬用サテン調塗料（チタン色）で処理した樹脂板の外観をＬ値で評価した結果１１３.４の値を示した。また、樹脂板は、一様な外観でサテン調のアルマイト色が付与されていた。 As a result of evaluating the appearance of the resin plate treated with the dipping satin-tone paint (titanium color) prepared in Example 5 as an L value, a value of 113.4 was shown. The resin plate was given a satin-like alumite color with a uniform appearance.
実　施　例　８
　　　サテン調塗装：
　Ｍ８－２５六角ボルト（表面は化成処理をした亜鉛メッキ）１０個を網かごに入れ、実施例１で調製した浸漬用サテン調塗料（ステンレス色）または実施例５で調製した浸漬用サテン調塗料（チタン色）に、３０秒程度浸漬し、引き上げた。次いで、網かごごとボルトを遠心乾燥機にて４００ｒｐｍで乾燥させ、更に１８０℃で２０分間焼成して、ボルトに表面処理を施した（膜厚は１μｍ程度）。塗料浸漬前のボルトと塗料浸漬後のボルトの外観を図２に示した。 Example 8
Satin paint:
Put 10 M8-25 hexagon bolts (the surface is galvanized with chemical conversion treatment) into a mesh basket and immerse the satin paint for immersion (stainless steel color) prepared in Example 1 or the satin paint for immersion prepared in Example 5. It was immersed in (titanium color) for about 30 seconds and pulled up. Subsequently, the bolts with the mesh cage were dried at 400 rpm with a centrifugal dryer, and further baked at 180 ° C. for 20 minutes, so that the bolts were subjected to a surface treatment (the film thickness was about 1 μm). The external appearance of the bolt before the paint immersion and the bolt after the paint immersion is shown in FIG.
　何れの塗料で処理したボルトも一様な外観でサテン調のアルマイト色が付与されていた。 The bolts treated with any paint had a uniform appearance and a satin-like anodized color.
試　験　例　１
　　　塩水噴霧試験：
　実施例８で得られたサテン調塗料で表面処理したボルトを、それぞれＪＩＳ　Ｚ　２３７１に従って塩水噴霧試験を行った。また、比較として未処理のボルトについても同様に塩水噴霧試験を行った。その結果を表１に示した。 Test example 1
Salt spray test:
The bolts surface-treated with the satin paint obtained in Example 8 were each subjected to a salt spray test in accordance with JIS Z 2371. For comparison, a salt spray test was also performed on untreated bolts. The results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　塩水噴霧試験の結果、未処理品が７４０時間にて赤錆が発生していたのに対し、本発明塗料を用いて表面処理したサテン調塗料表面処理品は、塩水噴霧試験２０００時間であっても大きな腐食は見られなかった。 As a result of the salt spray test, red rust was generated in the untreated product at 740 hours, whereas the satin-like paint surface-treated product treated with the paint of the present invention had a salt spray test of 2000 hours. There was no significant corrosion.
実　施　例　９
　　　サテン調塗装：
　マグネシウムの試験片について、実施例７と同様にしてサテン調塗装を行ったところ、一様な外観でサテン調のアルマイト色が付与される。 Example 9
Satin paint:
When a satin-like coating was applied to the magnesium test piece in the same manner as in Example 7, a satin-like alumite color was imparted with a uniform appearance.
実　施　例　１０
　　　サテン調塗装：
　銅の試験片について、実施例７と同様にしてサテン調塗装を行ったところ、一様な外観でサテン調のアルマイト色が付与される。 Example 10
Satin paint:
When a satin-like coating was applied to the copper test piece in the same manner as in Example 7, a satin-like alumite color was imparted with a uniform appearance.
　本発明の浸漬用サテン調塗料は、従来よりも薄い膜厚でも耐食性が得られ、しかも、浸漬する回数も一回で十分である。そのため、自動車部品等の大量に処理するのに好適である。
 
　　　　　　　　　　　　　　　　　　　　　　　　　　　　以　　上 The satin-like paint for dipping of the present invention can provide corrosion resistance even with a thinner film thickness than before, and is sufficient to be dipped once. Therefore, it is suitable for processing a large amount of automobile parts and the like.

more than

Claims (20)

  1. 　平均粒子径が１～５０μｍであり、平均片厚が５～５０ｎｍである金属薄片、シリコンオリゴマー、樹脂を含有することを特徴とする浸漬用サテン調塗料。 A satin-like paint for dipping characterized by containing metal flakes having an average particle diameter of 1 to 50 μm and an average piece thickness of 5 to 50 nm, a silicon oligomer, and a resin.
  2. 　シリコンオリゴマーがアルコキシシランオリゴマーである請求項１記載の浸漬用サテン調塗料。 The satin-like paint for immersion according to claim 1, wherein the silicon oligomer is an alkoxysilane oligomer.
  3. 　アルコキシシランオリゴマーがアルコキシシランと多価アルコールとの反応縮合物である請求項２記載の浸漬用サテン調塗料。 The satin paint for immersion according to claim 2, wherein the alkoxysilane oligomer is a reaction condensate of alkoxysilane and polyhydric alcohol.
  4. 　樹脂がアクリル樹脂、ウレタン樹脂、フェノール樹脂およびエポキシ樹脂からなる群から選ばれる１種または２種以上である請求項１記載の浸漬用サテン調塗料。 The satin paint for immersion according to claim 1, wherein the resin is one or more selected from the group consisting of an acrylic resin, a urethane resin, a phenol resin and an epoxy resin.
  5. 　金属薄片がアルミニウム薄片である請求項１記載の浸漬用サテン調塗料。 The satin-like paint for dipping according to claim 1, wherein the metal flakes are aluminum flakes.
  6. 　ディップ－スピン法用である請求項１～５の何れかに記載の浸漬用サテン調塗料。 The satin paint for immersion according to any one of claims 1 to 5, which is used for a dip-spin method.
  7. 　被処理部材を、請求項１～６の何れかに記載の浸漬用サテン調塗料に浸漬することを特徴とする表面処理方法。 A surface treatment method comprising dipping a member to be treated in the satin-like paint for dipping according to any one of claims 1 to 6.
  8. 　被処理部材の表面が、マグネシウムまたはマグネシウム合金である請求項７記載の表面処理方法。 The surface treatment method according to claim 7, wherein the surface of the member to be treated is magnesium or a magnesium alloy.
  9. 　被処理部材の表面が、亜鉛または亜鉛合金である請求項７記載の表面処理方法。 The surface treatment method according to claim 7, wherein the surface of the member to be treated is zinc or a zinc alloy.
  10. 　被処理部材の表面が、鉄、銅、ニッケル、コバルト、クロムおよびスズからなる群から選ばれる金属の１種または前記金属の２種以上を含む合金である請求項７記載の表面処理方法。 The surface treatment method according to claim 7, wherein the surface of the member to be treated is one type of metal selected from the group consisting of iron, copper, nickel, cobalt, chromium, and tin, or an alloy containing two or more types of the metal.
  11. 　被処理部材の表面が、アクリロニトリル・ブタジエン・スチレン共重合体、ポリカーボネート、ビスマレイミドトリアジンおよびポリイミドからなる群から選ばれる合成樹脂の１種または前記樹脂の２種以上からなる合成樹脂アロイである請求項７記載の表面処理方法。 The surface of the member to be treated is one type of synthetic resin selected from the group consisting of acrylonitrile / butadiene / styrene copolymer, polycarbonate, bismaleimide triazine and polyimide, or a synthetic resin alloy consisting of two or more types of the resins. 8. The surface treatment method according to 7.
  12. 　浸漬回数が１回である請求項７～１１の何れかに記載の表面処理方法。 The surface treatment method according to any one of claims 7 to 11, wherein the number of immersions is one.
  13. 　浸漬後に焼成するものである請求項７～１２の何れかに記載の表面処理方法。 The surface treatment method according to any one of claims 7 to 12, which is fired after immersion.
  14. 　被処理部材を、請求項１～６の何れかに記載の浸漬用サテン調塗料に浸漬して得られることを特徴とする表面処理製品。 A surface-treated product obtained by immersing a member to be treated in the satin-like paint for dipping according to any one of claims 1 to 6.
  15. 　被処理部材の表面が、マグネシウムまたはマグネシウム合金である請求項１４記載の表面処理製品。 The surface-treated product according to claim 14, wherein the surface of the member to be treated is magnesium or a magnesium alloy.
  16. 　被処理部材の表面が、亜鉛または亜鉛合金である請求項１４記載の表面処理製品。 The surface-treated product according to claim 14, wherein the surface of the member to be treated is zinc or a zinc alloy.
  17. 　被処理部材の表面が、鉄、銅、ニッケル、コバルト、クロムおよびスズからなる群から選ばれる金属の１種または前記金属の２種以上からなる合金である請求項１４記載の表面処理製品。 The surface-treated product according to claim 14, wherein the surface of the member to be treated is one kind of metal selected from the group consisting of iron, copper, nickel, cobalt, chromium, and tin, or an alloy composed of two or more kinds of the metals.
  18. 　被処理部材の表面が、アクリロニトリル・ブタジエン・スチレン共重合体、ポリカーボネート、ビスマレイミドトリアジンおよびポリイミドからなる群から選ばれる合成樹脂の１種または前記樹脂の２種以上からなる合成樹脂アロイである請求項１４記載の表面処理製品。 The surface of the member to be treated is one type of synthetic resin selected from the group consisting of acrylonitrile / butadiene / styrene copolymer, polycarbonate, bismaleimide triazine and polyimide, or a synthetic resin alloy consisting of two or more types of the resins. 14. The surface treatment product according to 14.
  19. 　浸漬回数が１回である請求項１４～１８の何れかに記載の表面処理製品。 The surface-treated product according to any one of claims 14 to 18, wherein the number of immersions is one.
  20. 　浸漬後に焼成するものである請求項１４～１９の何れかに記載の表面処理製品。
          The surface-treated product according to any one of claims 14 to 19, which is fired after immersion.
PCT/JP2015/070587 2015-07-17 2015-07-17 Satin finish immersion coating and surface treatment method using same WO2017013716A1 (en)

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JP2013119644A (en) * 2011-12-06 2013-06-17 Yuken Industry Co Ltd Rust-preventive coating
JP2014205909A (en) * 2013-03-19 2014-10-30 株式会社シールドテクス Rust preventive composition
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WO2014207885A1 (en) * 2013-06-28 2014-12-31 株式会社Ｊｃｕ Silicon oligomer and production method therefor

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JP2007015296A (en) * 2005-07-08 2007-01-25 Nippon Paint Co Ltd Design coating film and its forming method and coated article
JP2013119644A (en) * 2011-12-06 2013-06-17 Yuken Industry Co Ltd Rust-preventive coating
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JP2018076405A (en) * 2016-11-07 2018-05-17 株式会社イクヨ Metallic coating composition and coat

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