JP2012180544A - Glass coating agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a normal temperature glass coating agent which can be applied to the surface of a metal such as stainless steel at a so-called normal temperature of 200°C or less to thereby easily obtain the metal excellent in weather resistance, antifouling property, and flame retardancy.SOLUTION: The normal temperature glass coating agent contains boron ions and halogen ions as a catalyst required for making oxides and is composed of a single composition or a composite composition of a hydrolyzable organometallic compound dissolved in an alcohol. When the glass coating agent is applied to the surface of a metal plate, it can be dried at a so-called normal temperature of 200°C or less, and the metal surface can be made excellent in weather resistance, antifouling property, and flame retardancy.

Description

  The present invention relates to a glass coating agent. For example, a plate-like body excellent in weather resistance, antifouling property and flame retardancy can be easily obtained by applying it to the surface of a plate-like body such as a metal plate such as stainless steel. The present invention relates to a glass coating agent.

Conventionally, as a technique for coating a metal surface, as shown in Patent Document 1, powder glass (B ₂ O ₃ · PbO, SiO ₂ · PbO · B ₂ O ₃ , B ₂ is applied to the surface of a metal plate. An oxide material of O ₃ · ZnO · PbO, SiO ₂ · B ₂ O ₃ · SrO) is applied to a thickness of 50 μm to 1 mm, and heated and melted at 500 to 1100 ° C. to form an oxide layer on the surface. Are known. Moreover, the technique which manufactures a metal oxide glass film at what is called normal temperature of 200 degrees C or less is disclosed by patent document 2 and patent document 3. FIG.

JP-A-7-262860 JP-A-6-199528 JP 2000-164056 A

  However, since the coating agent shown in the above-mentioned conventional Patent Document 1 applies a powdery vitreous oxide substance to the surface of a metal plate and heats and melts it to form an oxide layer on the surface, It must be heated and melted at 500 to 1100 ° C. while paying close attention so that the oxided (vitrified) layer formed in consideration of the thermal expansion coefficient of the metal plate and glass is not curved. However, there is a disadvantage that it is a complicated process and very difficult.

  Moreover, since the coating agent shown by this patent document 1 has to process at high temperature, there existed a fault that processing equipment cost increased. Furthermore, in Patent Document 2 and Patent Document 3 described above, it is not planned at all to form an oxided (vitrified) layer on the surface of the plate at room temperature, and its structure and technology are not disclosed.

  The present invention has been made in order to solve the above-mentioned drawbacks, and its purpose is to apply it to the surface of a plate-like body such as stainless steel at room temperature, and it is excellent in weather resistance, antifouling property and flame retardancy. It is to provide a glass coating agent that can be made.

  As one means for achieving such an object, for example, a single hydrolyzable organometallic compound which is applied to the surface of a plate-like body and contains boron ions and halogen ions as catalysts necessary for oxidation and melted in alcohol. A glass coating agent having a composition or a composite composition.

  For example, the plate-like body is a metal plate and is applied to the surface of the metal plate. Alternatively, the layer thickness to be applied is 5.0 to 20.0 μm.

  For example, the application is performed on a primer layer formed on the surface of the plate-like body. Furthermore, for example, the application is performed by spraying, by brush or by roll.

  According to this invention, it can apply | coat to the surface of a plate-shaped object at normal temperature, and can obtain the coating state excellent in a weather resistance, antifouling property, and a flame retardance easily. At that time, since it does not require high-temperature heating / melting treatment, it has the feature that it is easy to produce a plate-like body excellent in weather resistance and the like, and it does not require high-temperature treatment equipment, so it is inexpensive. Can be manufactured.

FIG. 1 is a cross-sectional view when a glass coating agent according to an embodiment of the present invention is applied to the surface of a metal substrate. FIG. 2 is a cross-sectional view when the primary is applied to the surface of the metal substrate and the glass coating agent of the present embodiment is applied to the surface of the primary layer. FIG. 3 is a perspective view of an experimental apparatus for inspecting the characteristics of the present embodiment.

  Embodiments of the present invention will be described below with reference to the drawings. FIG. 1 is a cross-sectional view when a metal room temperature glass coating agent (hereinafter referred to as “coating agent”) 2 according to an embodiment of the present invention is applied to the surface of a metal substrate 1, FIG. These are sectional drawings when the primary 3 is apply | coated to the surface of the metal base | substrate 1, and the coating agent 2 of this Embodiment is apply | coated to the surface of the primary 3. FIG.

  1 and 2, a plate-like substrate 1 is made of, for example, metal used in various industrial fields. Specifically, it can be composed of a ferrous metal such as SUS or a non-ferrous metal such as an aluminum alloy.

  The primary 3 will be described before the description of the coating agent 2. The primary 3 is made of a well-known primary made of a silicate resin system, and the surface of the metal base 1 is mirror-like, and the surface of the base 1 is coated. Used when the adhesive / adhesiveness of the agent 2 is poor.

  The application of the primary 3 can be performed on the surface of the metal substrate 1 by spraying, brushing or roll coating, and the coating thickness is 5.0 to 20.0 μm. Therefore, when the surface of the metal substrate 1 is rough and the coating agent 2 is sufficiently fixed and adhered to the surface of the substrate 1, the application of the primary 3 is omitted.

  The coating agent 2 is sprayed, brushed or rolled on the surface of the metal substrate 1 as shown in FIG. 1 or on the surface of the primary 3 applied to the surface of the substrate 1 as shown in FIG. The coating is applied so that the coating thickness is 5.0 to 20.0 μm.

The coating agent 2 includes, for example, a main agent obtained by melting organosiloxane and organopolysiloxane containing silicon with a lower alcohol, an ammonium salt (for example, ammonium chloride (NH ₄ Cl)), and a boron ion generating material (for example, triethoxyborane). (B (Et) ₃ )) and a catalyst in which an organometallic compound (for example, metal alkoxide) containing Ti (titanium) and Sn (tin) is melted in a lower alcohol are melted in a ratio of, for example, 9 to 9 for the main agent. The resulting solution can be used as a coating agent diluted in a predetermined ratio with a diluting solvent.

The catalyst may be a fluorine compound (for example, sodium fluoride) instead of the ammonium salt. Furthermore, the organometallic compound containing Ti (titanium) and Sn (tin) is Ti (titanium). Instead of Sn (tin), an organometallic compound containing Zn (zinc), Al (aluminum), or the like may be used.
Further, the mixing ratio of the main agent and the catalyst is not limited to the above example, and can be appropriately changed within a range not to be liberated.

  By the way, as shown in [Formula 1], the organosilicon compound functional group R (methyl group, phenyl group, etc.) is hydrolyzed by moisture in the air. Then, the hydroxyl group of the organopolysiloxane generated by this reaction is attacked by the functional group of the crosslinking agent (organosiloxane having a functional side chain), as shown in [Formula 2]. Under the action of a catalyst, a dealcoholization reaction is caused to form a cured polysiloxane which is a polymer compound having a three-dimensional structure.

However, the coating agent 2 in one embodiment of the present invention is applied to the surface of the metal substrate 1 or to the surface of the primary 3 applied to the surface of the metal substrate 1 to form a film, A glass coating layer can be produced.
When this is expressed by a chemical reaction formula, it is expressed by the following [Formula 3], [Formula 4], [Formula 5] and [Formula 6].

In addition, the above catalyst produces a complex ion BX ₄ ⁻ from B ³⁺ and X ⁻ (halogen ion), and M (metal) of an organic compound (metal alkoxide) M (OR) n containing metal and B of BX ₄ ⁻ Causes a complex reaction MX _{n + 1} ⁻ , and then the complex ion MX _{n + 1} ⁻ is hydrolyzed, and the hydrolyzed M (OH) n is subjected to a dehydration condensation reaction. Thus, a metal oxide (glass) is obtained at room temperature.

  Hereinafter, an example of characteristic experiment results when the coating agent according to the present embodiment described above is formed on the surface of a metal plate will be described.

(Experimental Example 1) Material Combustion Test A specimen used in the material combustion test of Experimental Example 1 is a primer on a base material of a stainless steel (SUS) plate having a thickness of B5 plate (185 mm × 257 mm) having a thickness of 1.0 mm. And a coating agent applied. That is, in this specimen, after applying a silicate resin primer on one side of a substrate, it is dried at 60 ° C. or more for 60 minutes or more, and then the coating agent according to the present invention is applied to the primer surface at 60 ° C. or more. It was obtained by drying for 60 min or more.

  In the above example, a primer and a coating agent are applied to a stainless steel plate having a thickness of 1.0 mm. However, the material and thickness of the plate to be applied are not limited, and any metal, plastics, carbon fiber, etc. The material is not limited, and the thickness is not limited at all.

  Two specimens were prepared, one of which was controlled so that the film thickness at the time of vitrification was about 5.0 μm by applying a coating agent consisting of one solution in which the main agent and catalyst were diluted with a diluent solvent. The coating film A is a specimen, and the other is a film at the time of vitrification by applying a coating agent consisting of two liquids obtained by diluting the coating agent consisting of the main agent and catalyst of this embodiment with alcohol. This is a specimen of “Coating B” having a thickness of about 20.0 μm.

  The material combustion test on the coated surface was performed using the experimental apparatus shown in FIG. This experimental apparatus is configured by providing a pair of support pieces 11a and 11b on the substrate 10 so that both sides of the specimen S are inclined at an inclination angle of 45 degrees and the coating agent application surface faces downward. The container base 13 is provided so that the combustion container 12 is positioned in the vertical direction 25.4 (1 inch) mm at the center of the lower surface of the specimen S placed on the support pieces 11a and 11b. The combustion container 12 has a structure of 17.5φ × 71 1, 0.8 t and is placed on a container base 13 with a cork plate 14 having a low thermal conductivity interposed. The material combustion test is performed by leaving the 0.5 cc pure ethyl alcohol put in the combustion container 12 to burn out.

  In addition, when the specimen is made of a hygroscopic material, a specimen finished to a predetermined size is used in a room with air permeability, away from direct sunlight, separated from the floor by 1 m or more and allowed to elapse for 5 days or more. . This material combustion test is performed under conditions where the temperature in the test chamber is 15 to 30 ° C., the humidity is 60 to 75%, and there is no air flow.

  [Table 1] shows the results of a material combustion test performed using the above-described experimental apparatus. This material combustion test was conducted by the Japan Railway Vehicle Machinery Technology Association (location: 1-19-4 Shimbashi, Minato-ku, Tokyo, combustion test room, person in charge: Muto). Judgment of this combustion test is carried out separately during and after alcohol combustion. During combustion, the specimen is observed for ignition, ignition, smoke generation, flame condition, etc. This is done by investigating residual dust, carbonization and deformation state.

(Experimental example 2) Xenon arc lamp accelerated weather resistance test This xenon arc lamp accelerated weather resistance test was performed using the two specimens S of "coating film A" and "coating film B" described above. The xenon arc lamp is a light source that generates a wavelength that matches the sunlight over the ultraviolet and visible regions, and can perform an accelerated weathering test in a state very close to the actual situation of outdoor equipment.

  In this test method, ultraviolet rays (300 to 400 nm) are irradiated for 600 hours, 1200 hours are irradiated, and humidity is adjusted (temperature 70 ° C./48 min at 10% humidity, temperature 50 ° C./12 min at 80% humidity). This is done by measuring and measuring the deterioration rate. The 600-hour irradiation corresponds to the actual equipment used for 4 years, and the 1200-hour irradiation corresponds to the actual equipment used for 8 years. In addition, the unit of the numerical value in the table before and after coating, 600 hour irradiation and 1200 hour irradiation is%.

The main uses in this test are as follows.
a. Light irradiation test / light source-xenon arc lamp (7.5Kw water-cooled x 3 lights)
b. Applicable test temperature and humidity range Light irradiation (temperature 40-70 ± 2 ° C, temperature 30-60 ± 5%)
Acid rain (temperature 35-50 ± 2 ° C, no temperature limit)
Drying (temperature 20-80 ± 2 ° C, no temperature limit)
Wet (temperature 50-95 ± 5% at temperature 50-60 ° C)
Condensation (temperature 40-50 ± 2 ° C, temperature 95 ± 5%)
Low temperature (temperature -20-20 ± 2 ° C)
c. Test chamber dimensions (width 350cm x depth 308cm x height 176cm)
d. Four spray towers in the test tank [Table 2] shows the results of the accelerated weather resistance test.

(Experimental example 3) Antifouling property test This antifouling property test was performed by writing letters with an oil-based marking pen on the application surfaces of the two specimens "Coating film A" and "Coating film B" described above. It was done by whether or not the written characters could be erased. [Table 3] shows the results of the antifouling test (oil-based marking pen test).

(Experimental example 4) Scratch-proof test This scratch-proof test is a bamboo skewer, a plastic stick, H5 pencil, and H5 lead on the coating surface of the two specimens S of "coating film A" and "coating film B". Each brush was rubbed at normal pen pressure. [Table 4] shows the results of the scratch resistance test (scratch test).

(Experimental example 5) Simple falling ball / falling weight impact test This impact test is performed by using a well-known metal punch (48 g) on the coating surface of the two specimens S, "coating film A" and "coating film B". ) And a steel ball having a diameter of 19 mm. The drop weight impact test using a punch was performed by dropping vertically from a height of 30 cm. In [Table 5], the drop weight impact test of “* 1” was shown. The impact test is performed by vertically dropping from a height of 90 cm, and is shown as “* 2” simple falling ball / falling weight drop test in [Table 5].
[Table 5] shows the results of the falling ball / falling weight impact test (drop test).

The coating film A (coating film thickness; 20.0 μm) and coating film B (coating film thickness; 5.0 μm) according to the present embodiment are nonflammable and accelerated weather resistance according to the results of the material combustion test described above. From the results of the property test, it is understood that the glossiness is increased about 3 times by applying the coating agent as compared with that before the application. In addition, it can be seen that the gloss rate is reduced by 10% at 600 hours of UV irradiation and the gloss rate is reduced by 20 to 50% at 1200 hours of UV irradiation, but it is maintained approximately twice as much as that in the case of no application.
The glossiness is defined as “100% of refractive index 1.576”.
Further, it was found that the organic coating film C gave a result that was not better than the uncoated glossiness.

  According to the results of the antifouling test, it is possible to perform a cleaning process by applying a coating agent as compared to the case of no application, and further, according to the results of the scratch resistance test and the simple falling ball / falling weight impact test. , You can see that it is difficult to scratch. In addition, it can be seen that a metal having excellent weather resistance, antifouling properties and flame retardancy can be obtained with a coating thickness of 5.0 to 20.0 μm.

The coating agent according to the present invention can be employed as a metal coating agent used in various industrial fields. Specifically, it is used for metal parts of vehicles such as trains and automobiles, metal parts of ships, gates such as elevators and home doors, metal parts of home appliances such as microwave ovens, metal ornaments, metal Buddhist tools, etc. can do.

1 …… Metal substrate 2 …… Normal temperature glass coating agent (coating agent) for metal
3 ... Primary 10 ... Substrate 11a, 11b ... Supporting piece 12 ... Combustion vessel 13 ... Container stand 14 ... Cork plate

Claims (5)

  It is characterized by comprising a single composition or a composite composition of a hydrolyzable organometallic compound melted in alcohol, containing boron ions and halogen ions as catalysts necessary for the oxidation, applied to the surface of the plate-like body. Glass coating agent.   2. The glass coating agent according to claim 1, wherein the plate-like body is a metal plate and is applied to the surface of the metal plate.   The glass coating agent according to claim 1 or 2, wherein the applied layer thickness is 5.0 to 20.0 µm.   The glass coating agent according to any one of claims 1 to 3, wherein the application is performed on a primer layer formed on a surface of the plate-like body.   The glass coating agent according to any one of claims 1 to 4, wherein the application is performed by spraying, by a brush, or by a roll.

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