JPH0133511B2 - - Google Patents

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention relates to a synthetic resin paint containing stainless steel foil powder, particularly a stainless steel coated with a surface treatment to improve the wettability between the stainless steel and the synthetic resin. This invention relates to a synthetic resin paint containing steel foil powder. <Prior art and its problems> The purpose of painting is to maintain the beauty of the object to be coated and to prevent corrosion when the object to be coated is steel. Modern large steel structures such as ships, bridges, cranes, and chimneys are not only aesthetically pleasing, but also have an emphasis on corrosion prevention and are becoming maintenance-free. This is because the weight of paint costs in the total painting cost has decreased, and the cost of painting, including scaffolding, has increased significantly, so it is better to use more durable paint, extend the interval between coats, and reduce the number of coats. This is because there are merits. Furthermore, there are other advantages such as reducing the number of dangerous high-place work operations during painting work, and avoiding a decrease in the operating rate of equipment due to painting work. It is well known that stainless steel has good corrosion resistance and durability. However, stainless steel is expensive. For this reason, although it is thought that paints containing stainless steel powder should have excellent performance, the reason why they have not been put into full-scale use is that stainless steel powder and foil pieces are not easy to manufacture and are expensive. In addition to economic reasons, such as the fact that paints containing this material are significantly more expensive than conventional paints, it is also clear from the fact that there is no paint that adheres well to stainless steel. There was a technical reason that the wettability of synthetic resins to stainless steel was poor, and as a result, even if stainless steel foil powder was contained, the original performance of stainless steel could not be demonstrated. The present inventors have discovered that by treating stainless steel with a certain type of surface treatment agent, the wettability between stainless steel and various synthetic resins is significantly improved, and as a result,
Corrosion resistance that was unimaginable with conventional paint applications,
It has been found that not only durability is achieved, but also thicker coating is possible compared to conventional stainless steel paints, and workability is improved. While conventional anticorrosive paints have a lifespan of 5 to 7 years, the synthetic resin paint containing stainless steel foil powder according to the present invention has a lifespan of over 20 years, and with existing stainless steel paints, it can last for one time. The coating film is at most 10~
15 μm, but this synthetic resin paint containing stainless steel foil powder has the advantage of being able to obtain a coating film of 25 to 30 μm in one coat, which greatly contributes to reducing work costs and is extremely effective. Become. <Object of the Invention> Therefore, the object of the present invention is to provide a stainless steel foil powder that has high wettability with various synthetic resins on stainless steel, can be coated thickly, and has significantly improved corrosion resistance and durability. The aim is to provide a synthetic resin paint containing the same. <Structure of the Invention> The above object is achieved by the following present invention. That is, in the present invention, stainless steel foil powder that has been surface-treated with a surface treatment agent of 0.1 to 5% by weight based on the total weight of the stainless steel foil powder is added to a synthetic resin to cover all of the dried coating film. 20~80% by weight
A synthetic resin paint containing stainless steel foil powder is provided. Hereinafter, the synthetic resin paint containing stainless steel foil powder of the present invention will be explained in detail. The synthetic resins used in the present invention may be generally known synthetic resins that are normally used in paints, such as alkyd resins, aminoalkyd resins, chlorinated rubber, vinyl chloride resins, polyvinyl butyral resins, silicone resins, and polyester resins. resin,
Examples include acrylic resin, polyurethane resin, epoxy resin, phenolic resin, and fluororesin. More specifically, the alkyd resins include phthalic acid resins that contain almost no oils and fats, and alkyd resins that contain oils and oils and are short, medium, long, and very long. Amino alkyd resin is composed of urea resin or melamine resin and alkyd resin, and is usually used in baking paints. Chlorinated rubber includes chlorinated natural rubber, synthetic rubber, and those modified with alkyd resins. Vinyl chloride resin is a copolymer of vinyl chloride and vinyl acetate. Polyvinyl butyral resin is made by saponifying polyvinyl acetate to form polyvinyl alcohol, which is then reacted with butyraldehyde, and is considered to be a terpolymer of acetal, vinyl alcohol, and vinyl acetate. Silicone resin is a polymeric compound consisting of silicon and oxygen that contains methyl and phenyl groups as organic groups, and includes those modified with alkyd resins, epoxy resins, and the like. Polyester resins are unsaturated polyester resins, including those crosslinked with vinyl monomers such as styrene. Acrylic resins include methacrylic ester polymers used in lacquer types and copolymers of styrene and acrylamide acrylic acid esters used in lacquer types, as well as those modified with alkyd resins and urethane resins. Polyurethane resins are composed of polyisocyanate compounds and polyol compounds, and include block types, catalyst curing types, and polyol curing types. Polyols include those obtained by the reaction of epoxy resins, polyhydric alcohols, and alcohol amines. , and acrylic polyols. The epoxy resin may be a so-called bisphenol A type, a bisphenol F type, a volcanic type epoxy, or an epoxy resin, and the curing agent may be a known curing agent.
Examples include polyamide resins, polyamines, adducts thereof, modified products thereof, and anhydrides of phthalic anhydrides. Phenol resin is 100% carbonic acid resin, modified carbonic acid resin with rosin, etc. Examples of the fluororesin include polytetrafluoroethylene (Teflon) and tetrafluoroethylene. The surface treatment agent for stainless steel foil powder according to the present invention is a combination of one or more selected from titanate coupling agents, silane coupling agents, and nonionic coupling agents. Specifically, titanate coupling agents include:
Isopropyl triisostearoyl titanate,
Examples include isopropyl tridodecylbenzenesulfonyl titanate, tetra(2,2-diallyloxymethyl-1-butyl)bis(di-tridecyl)phosphite titanate, and silane coupling agents include vinyltrichlorosilane and vinyltriethoxysilane. , vinyltris(β-methoxyethoxy)silane, etc., and nonionic coupling agents include polyoxyethylene laurate, polyoxyethylene stearate, polyoxyethylene oleate, etc. Although these surface treatment agents alone are effective, the combination of stainless steel and synthetic resins
Also, depending on the type of solvent and other additives that make up the paint, a combination of several types may be more effective. These surface treatment agents have a coupling effect, an affinity effect, and a cilia effect on stainless steel and synthetic resins, so that the stainless steel is better wetted by the synthetic resin, and the stainless steel foil powder is better wetted by the synthetic resin. Molding a deciduous sedimentary layer in the resin,
A strong coating film is formed. The above surface treatment agent is suitable for stainless steel foil powder.
A proportion is selected within the range of 0.1 to 5% by weight that does not affect other additives. If the amount of surface treatment agent based on the stainless steel foil powder is less than 0.1% by weight, the adhesion with the resin will be poor;
This is because if the content exceeds this value, the dispersibility in the resin will decrease. One or more types of stainless steel foil powder may be used in combination. The shape of the stainless steel foil powder used in the present invention is 0.1 to 0.5 microns thick, 10 to 30 microns long,
Ultra-thin pieces with a width of 5 to 20 microns are preferred, and those with a large aspect ratio (diameter:thickness) are effective. The type of stainless steel is one that has excellent corrosion resistance, weather resistance, chemical resistance, wear resistance, etc.
Not limited to JIS G4301, 4302
It is sufficient to appropriately select a steel type that is suitable for the object to be painted, environmental conditions, etc. from the stainless steel specified in the above. Generally known solvents or non-reactive diluents can be used in the synthetic resin paint containing stainless steel foil powder according to the present invention. Examples of these solvents include aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as mineral turbene,
Ketones such as methyl ethyl ketone and methyl isobutyl ketone, esters such as ethyl acetate and butyl acetate, and mixtures thereof; non-reactive diluents include petroleum resins;
Examples include indencoumarone resin. Generally known paint additives can be used in the synthetic resin paint containing stainless steel foil powder according to the present invention. For example, organic bentonite, thixotropic agents such as anhydrous silicic acid powder, metal soaps, hydrogenated castor oil, anti-settling agents such as synthetic waxes mainly composed of ethylene oxide, dryers for alkyd resins,
Effect accelerators such as tertiary amines for epoxy resins may be added as necessary. The blending ratio of stainless steel foil powder, synthetic resin, and surface treatment agent in the synthetic resin paint containing stainless steel foil powder according to the present invention is in the range of 20 to 80% by weight in the dry coating film. Make a selection. This is because if the amount of stainless steel foil powder in the dried coating film is less than 20% by weight, the strength of the coating will be poor due to insufficient foil powder, and if it exceeds 80% by weight, the coating will not be formed due to insufficient resin. The functional differences between the conventional paint and the paint according to the present invention will be briefly explained with reference to FIGS. 1 and 2. FIG. 1 shows the change over time of a conventional paint. Figure 1a shows the resin 2 immediately after coating on the substrate 1.
Paint particles are dispersed inside. At the middle stage of drying as shown in FIG. 1b, degassing passages 4 for solvent and the like begin to form, and the surface begins to shrink. At the completion of drying as shown in Fig. 1c, a degassing channel 4 is formed in the coating film thickness, which expands due to external factors, and the coating film gradually deteriorates and its lifespan is shortened, so repainting is required in a short period of time. I have to do it. FIG. 2 shows the change over time of the paint according to the present invention. Figure 2a shows the state immediately after coating on the substrate 1,
Surface-treated stainless steel foil powder 5 in resin 2
are dispersed. Since the stainless steel foil powder has been surface-treated, it has good compatibility with the resin 2 and the substrate 1, that is, good wettability, resulting in good adhesion. Additionally, it can be applied thicker and without dripping than conventional coatings. Figure 2b shows the leveling of the coating film, and the stainless steel foil powder 5, which was oriented in various directions immediately after painting in Figure 2a, now faces horizontally in the same direction within the layer of resin 2. They are aligned and overlap each other. Although the degassing passage 4 is formed through the gaps between these stainless steel foil powders 5, it becomes a complicated passage. FIG. 2c shows the dry state, in which several layers (actually 3 to 7 layers) of stainless steel foil powder 5 overlap within the layer of resin 2. Therefore, the degassing path 4 becomes unclear, and there is virtually no deterioration of the coating from this part, and the superimposed layer of stainless steel foil powder 5 guarantees corrosion resistance and durability, resulting in a long service life and reuse. Since it takes a long time to paint, it is possible to reduce costs. <Examples> Next, the present invention will be specifically described with reference to Examples and Comparative Examples. [Example 1-1] 350 parts by weight of an epoxy resin having an epoxy equivalent of 180 to 200 (Epicoat #828, manufactured by Yuka Shell Co., Ltd.) was thoroughly kneaded by a conventional method. Next, stainless steel foil powder (SUS316L, thickness 0.1~
Add 330 parts by weight of 0.5 μm, 5 to 20 μm in width, 10 to 30 μm in height, mix and stir in the usual manner to disperse the stainless steel foil powder in the epoxy resin, and form Paint A-1.
1000 parts by weight of liquid was obtained. 550 parts by weight of an epoxy curing agent (Ratsucarmide TD-966-H, Dainippon Ink Co., Ltd.) and 450 parts by weight of a solvent such as butyl cellosolve were mixed and thoroughly kneaded by a conventional method to obtain 1000 parts by weight of Paint B-1. A mixed paint made by mixing paint A-1 liquid and paint B-1 liquid in a ratio of 100/50 by weight was able to be applied in one coat to a dry film thickness of 40 to 50 μm without dripping by ordinary airless spraying. This mixed paint was coated to a dry film thickness of 50 μm according to JISK5400, and tested according to JISK-5400 with a pencil scratch test, boiling water resistance, acid resistance (5% sulfuric acid solution), and alkali resistance (5% caustic soda solution). ), a salt spray test was conducted. The results are shown in Table 1. [Example 1-2] Same as Example 1-1 except that 2 parts by weight of γ-methacryloxypropyltrimethoxysilane was used instead of 2 parts by weight of isopropyl dimethacrylylisostearoyl thiranate in Example 1-1. A paint A-2 liquid was obtained. Paint B-1 was obtained in exactly the same manner as in Example 1-1. Paint A-2 liquid/Paint B-1 liquid 100 parts by weight/
The mixed paint mixed at a ratio of 50 was able to be applied in one coat to a dry film thickness of 40 to 50 μm without sagging using normal airless spraying. The same test as in Example 1-1 was conducted on this mixed paint. The results are shown in Table 1. [Comparative Example 1-1] Same as Example 1-1 except that Example 1-1 and isopropyl dimecrylisostearoyl thiranate and γ-methacryloxypropyltrimethoxysilane of Example 1-2 were not used. Paint A
-3 liquids were obtained. Paint B-1 liquid was obtained in exactly the same manner as in Example 1-1. Paint A-3 liquid/Paint B-1 liquid 100 parts by weight/
The mixed solution mixed at a ratio of 50 can be sprayed with normal air to a dry film thickness of 10 to 15 without dripping.
I couldn't paint it with a coat. The same test as in Example 1-1 was conducted on this mixed paint. The results are shown in Table 1. [Comparative Example 1-2] A commercially available epoxy resin paint, Kopon P manufactured by Nippon Paint, was applied as a primer with a dry film thickness of 60 μm + a top coat dry film thickness of 35 μm at predetermined intervals, and the same test as in Example 1-1 was conducted. Ivy. Table 1 shows the results.
Shown below. [Example 2-1] 550 parts by weight of medium oil alkyd resin, 147 parts by weight of a solvent such as xylene, and 3 parts by weight of an anti-settling agent,
The mixture was thoroughly kneaded by a conventional method. Next, stainless steel foil powder (SUS316L) treated with 2 parts by weight of isopropyl tridodecylbenzene sulfonyl titanate was added.
Add 300 parts by weight (thickness 0.1 to 0.5 x width 5 to 20 μm, height 10 to 30 μm), mix and stir in the usual manner, and uniformly disperse the stainless steel foil powder in the alkyd resin.Paint C-1 1000 parts by weight I got the department. This paint C-1 could be applied in one coat with a normal airless sprayer to a dry film thickness of 40 to 50 μm without dripping. This paint has a dry film thickness of 50 μm according to JISK5400.
Pencil scratch tests, boiling water resistance, acid resistance (5% sulfuric acid solution), alkali resistance (5% caustic soda solution), and salt water spray tests were conducted according to JISK5400. The results are shown in Table 1. [Example 2-2] Same as Example 2-1 except that 2 parts by weight of γ-glycidoxy propyl trimethoxysilane was used instead of 2 parts by weight of isopropyl tridodecylbenzene sulfonyl titanate in Example 2-1. Paint C-2 was obtained in the same manner. This paint C-2 could be applied in one coat to a dry film thickness of 40 to 50 μm without dripping using a regular airless sprayer. The same test as in Example 2-1 was conducted on this paint C-2. The results are shown in Table 1. [Comparative Example 2-1] Isopropyl tridodecylbenzene sulfonyl titanate of Example 2-1, Example 2-2
Paint C-3 was obtained in the same manner as in Example 2-1, except that γ-glycidoxy propyl trimethoxysilane was not used. This paint C-3 could only be applied in one coat to a dry film thickness of 10 to 15 μm using a regular airless sprayer without dripping. This paint C-3 was subjected to the same test as in Example 2-1. The results are shown in Table 1. [Comparative Example 2-2] Commercially available alkyd resin paint, Kanae Sabiz A
The same test as in Example 2-1 was conducted by applying two coats of primer x dry film thickness of 25 μm/time + one coat of top coat of dry film thickness of 50 μm at predetermined intervals. The results are shown in Table 1. 【table】

[Brief explanation of drawings]

Figures 1a, 1b and 1c are diagrammatic cross-sectional views showing the conventional paint immediately after application, in the middle of drying, and at the end of drying, respectively. Figure 2a, 2nd
Figures b and 2c are diagrammatic cross-sectional views showing the stainless steel foil powder-containing paint according to the present invention immediately after application, at the time of leveling the paint film, and at the time of completion of drying, respectively. Explanation of symbols, 1...Substrate, 2...Resin, 3...
Coating particles, 4... Degassing path, 5... Stainless steel foil powder.

Claims (1)

[Claims] 1 0.1 to total weight of stainless steel foil powder
Stainless steel, characterized in that stainless steel foil powder surface-treated with 5% by weight of a surface treatment agent is contained in a synthetic resin in an amount of 20 to 80% by weight based on the total weight of the dry coating film. Synthetic resin paint containing steel foil powder.