JP3909454B2 - Anti-rust pigment - Google Patents

Description

【００３２】
被塗板 ：Ｍｇ合金 ＡＺ３１ （日本テストパネル製）
塗装 ：バーコーター
硬化条件：焼き付け温度 ２１０℃（物温）
膜厚 ：２５μｍ
分散 ：ペイントコンディショナー
【００３３】
試験項目：塩水噴霧試験（５点満点）
上記の塗装条件で被塗板上に塗膜を形成することによって作成した試験板を、槽内温度を３５℃に保った塩水噴霧試験器内に静置して、５％塩化ナトリウム水溶液を１ｋｇ／ｃｍ² の圧力で４０時間塗膜に噴霧し、腐食状況を観察して以下の評価基準に基づき評価した。腐食状況は平面部の錆の発生面積で評価した。
いずれの評価においても、評価点が高いほど防錆能が優れている。
【００３４】
サビ発生防止効果の評価基準（ＡＳＴＭ Ｄ６１０−６８(1970)に準拠）
平面部
サビ発生面積 ０．１％未満 ： ５点
サビ発生面積 ０．１％以上〜１％未満 ： ４点
サビ発生面積 １％以上〜１０％未満 ： ３点
サビ発生面積 １０％以上〜３３％未満 ： ２点
サビ発生面積 ３３％以上 ： １点
【００３５】
試験例２：アルミニウム素材に対する防錆試験
実施例および比較例（ブランクおよび市販防錆顔料）の顔料を用いて下表に示す配合組成の焼き付け型エポキシ樹脂系塗料を調製し、塗膜形成後、糸錆試験を実施した。
【００３６】

【００３７】
被塗板 ：ＪＩＳ Ｈ４０００（Ａ２０２４Ｐ）Ｃ（日本テストパネル製）
塗装 ：バーコーター
硬化条件：焼き付け温度 ２１０℃（物温）
膜厚 ：２０μｍ
分散 ：ペイントコンディショナー
【００３８】
試験項目：糸錆試験（５点満点）
上記の塗装条件で被塗板上に塗膜を形成することによって作成した試験板に、カッターナイフで被塗板表面に達するクロスカットを入れ、槽内温度を３５℃に保った塩水噴霧試験器内に静置して、５％塩化ナトリウム水溶液を１ｋｇ／ｃｍ² の圧力で２４時間塗膜に噴霧した後、この試験板を水洗し、その後槽内温度４０℃−湿度８５％に調節した恒温恒湿機内に１０００時間静置して、糸錆の発生状況を観察し、以下の評価基準に基づき評価した。なお、糸錆の発生状況はカット部からの糸錆の長さで評価した。
【００３９】
糸錆の長さ ５ｍｍ未満 ： ５点
糸錆の長さ ５ｍｍ以上 〜 ８ｍｍ未満 ： ４点
糸錆の長さ ８ｍｍ以上 〜 １１ｍｍ未満 ： ３点
糸錆の長さ １１ｍｍ以上 〜 １４ｍｍ未満 ： ２点
糸錆の長さ １４ｍｍ以上 〜 １７ｍｍ未満 ： １点
糸錆の長さ １７ｍｍ以上 ： ０点
【００４０】

【００４１】

【００４２】
試験例３：亜鉛メッキ鋼板に対する防錆試験
実施例および比較例の顔料（ブランクおよび市販防錆顔料）を用いて下表に示す配合組成の焼き付け型ポリエステル樹脂系塗料を調製し、塗膜形成後、塩水噴霧試験を実施した。
【００４３】

【００４４】
被塗板 ：亜鉛メッキ鋼板 ＳＧＣＣ （日本テストパネル製）
塗装 ：バーコーター
硬化条件：焼き付け温度 ２１０℃（物温）
膜厚 ：１０μｍ
分散 ：ペイントコンディショナー
試験項目：塩水噴霧試験（１５点満点）
【００４５】
上記の塗装条件で被塗板上に塗膜を形成することによって作成した試験板に、カッターナイフで被塗板表面に達するクロスカットを入れ、槽内温度を３５℃に保った塩水噴霧試験器内に静置して、５％塩化ナトリウム水溶液を１ｋｇ／ｃｍ² の圧力で５６日間塗膜に噴霧し、錆発生状況および塗膜の膨れを観察して、以下の評価基準に基づき評価した。
なお、腐食状況は平面部の膨れと錆の発生面積、並びにカット部の腐食幅で評価した。
いずれの評価においても、評価点が高いほど防錆能が優れている。
【００４６】
サビ発生防止効果の評価基準（ＡＳＴＭ Ｄ６１０−６８(1970)に準拠）
───────────────────────────────────
平面部
サビ発生面積 ０．１％未満 ： ５点
サビ発生面積 ０．１％以上〜１％未満 ： ４点
サビ発生面積 １％以上〜１０％未満 ： ３点
サビ発生面積 １０％以上〜３３％未満 ： ２点
サビ発生面積 ３３％以上 ： １点
───────────────────────────────────
フクレ発生防止効果の評価基準（ＡＳＴＭ Ｄ７１４−５９(1965)に準拠）
───────────────────────────────────
平面部
８Ｆ以下 ： ５点
８Ｍ，６Ｆ ： ４点
８ＭＤ，６Ｍ，４Ｆ ： ３点
８Ｄ，６ＭＤ，４Ｍ，２Ｆ ： ２点
６Ｄ，４ＭＤ以上、２Ｍ以上 ： １点
カット部、端面部
腐食幅 ０〜１ｍｍ ： ５点
腐食幅 １〜２ｍｍ ： ４点
腐食幅 ２〜３ｍｍ ： ３点
腐食幅 ３〜４ｍｍ ： ２点
腐食幅 ４〜５ｍｍ ： １点
腐食幅 ５ｍｍ以上 ： ０点
───────────────────────────────────
【００４７】

【００４８】

[0001]
【Technical field】
The present invention relates to rust preventive pigments, in particular for non-ferrous metals such as zinc, magnesium, aluminum and their alloys, or steel materials plated with these non-ferrous metals.
[0002]
[Prior art and issues]
Non-ferrous metals such as zinc, magnesium, aluminum and their alloys are used as members of various structures and equipment and for plating steel materials such as steel plates. These non-ferrous metals are generally easily corroded, so that a primer containing a rust preventive pigment is coated on the surface.
[0003]
The rust preventive pigment used for this purpose was a chromate pigment such as strontium chromate, but development of a non-toxic rust preventive pigment has been demanded due to concerns about the toxicity of hexavalent chromium.
[0004]
In order to satisfy this demand, the present inventors disclosed a rust preventive pigment for a galvanized steel sheet made of amorphous magnesium silicate powder having a certain Mg / Si atomic ratio in Japanese Patent Application No. 11-078083. Anti-corrosive pigments that can be used for non-ferrous metals and their plated products are desired.
[0005]
[Disclosure of the present invention]
According to the present invention, from the amorphous alkaline earth metal silicate coprecipitate powder particles having an atomic ratio of M / Si (M is Ca, Sr or Ba) of 0.025 to 1.0. A rust preventive pigment is provided. This pigment exhibits an excellent anticorrosive action against non-ferrous metal materials such as zinc, magnesium, aluminum and alloys thereof or steel materials plated with the non-ferrous metal. The atomic ratio is more preferably 0.025 to 0.8.
[0006]
[Details]
The amorphous silicates of Ca, Sr and Ba having the atomic ratio are obtained by reacting an alkali metal silicate and a water-soluble salt of each alkaline earth metal in an aqueous solution at a ratio so as to achieve the atomic ratio. The produced precipitate can be produced by filtering, washing with water, drying and grinding. This is because, for example, an aqueous solution of potassium silicate or sodium silicate and an aqueous solution of a chloride of Ca, Sr or Ba or other water-soluble salt are prepared in advance, and these are mixed and stirred at the above-mentioned atomic ratio to form a precipitate Can be separated by filtration, washed with water, dried and then pulverized. In this case, when the charged atomic ratio is 0.4 or more or 0.2 or less, the total amount of alkaline earth metal and Si components charged may not precipitate and may remain in the mother liquor. By adding a strong base such as sodium hydroxide, in the latter case by adding a strong acid, preferably an acid having the same anion as the water-soluble alkaline earth metal salt, and coprecipitating the unreacted components as a hydrous oxide. An object substantially matching the charged atomic ratio is obtained.
[0007]
The anticorrosive pigment of the present invention is generally a white powder hardly soluble in water, and is used for corrosion protection of zinc and its alloys, Mg and its alloys, aluminum and its alloys, or steel plates plated with zinc or zinc alloys. It can be used by blending it with a paint intended for rust prevention.
[0008]
The rust preventive pigment of the present invention is more advantageous than the strontium chromate pigment in that the rust preventive pigment is almost comparable to the strontium chromate pigment, does not contain toxic heavy metals, and is white, so that the color of the paint is easy.
[0009]
Manufacture of the coating material using this pigment can be performed by a conventional method. The paint used in this field is a baking type, that is, a paint of a type in which a resin having a functional group is crosslinked and cured by an external curing agent. Such resin and curing agent combinations are well known in the paint industry. Examples include oil-free polyester resins, alkyd resins, acrylic polyol resins, or systems in which these modified resins are crosslinked and cured using aminoplast resins (typically melamine resins) or blocked isocyanates, bisphenol type or novolac type epoxy resins. A thermosetting epoxy system that cures using an acid anhydride, polyamine, or amino plus resin is included.
[0010]
The paint is blended so that the coating contains 5 to 40 wt%, particularly 10 to 30 wt% of the rust preventive pigment of the present invention. The paint contains an organic solvent, a catalyst such as an aromatic sulfonic acid acid catalyst in the case of a melamine resin curing agent, an organic tin compound in the case of a blocked isocyanate curing agent, a coloring pigment, an extender pigment, and a conventional paint additive. Of course. Since the technology for forming a paint including the above is well known and does not constitute a part of the present invention, further explanation will be unnecessary.
[0011]
【Example】
The following examples are for purposes of illustration and not limitation. In terms of composition and formulation,% is by weight.
[0012]
1. Manufacture of pigments <Calcium-based>
Example 1 Ca / Si = 1/1 = 1.0
400 mL of water was put into a 1 L beaker, and 17.4 g of anhydrous calcium chloride was dissolved. In another 200 mL beaker, 32.4 g of No. 3 water glass (SiO ₂ 29%, Na ₂ O 9.4%) was added, and 75 mL of water was added to make a diluted solution. This solution was stirred into the above calcium chloride solution, It poured in in 10 minutes, and also 28.7 g of 30% -NaOH aqueous solution was added similarly.
After pouring, the mixture was stirred for 30 minutes, and the resulting reaction precipitate was filtered and washed with water, dried at 110 ° C. overnight, and pulverized to obtain 21.0 g of a white powder. As a result of fluorescent X-ray analysis, this white powder was Ca / Si = 0.97, and the X-ray diffraction was amorphous.
[0013]
Example 2 Ca / Si = 4/5 = 0.8
400 mL of water was put into a 1 L beaker, and 13.9 g of anhydrous calcium chloride was dissolved. In another 200 mL beaker, 32.4 g of No. 3 water glass (SiO ₂ 29%, Na ₂ O 9.4%) was added, and 75 mL of water was added to make a diluted solution. This solution was stirred into the above calcium chloride solution, It poured in in 10 minutes, and also 20.3g of 30% -NaOH aqueous solution was added similarly.
After pouring, the mixture was stirred for 30 minutes, and the resulting reaction precipitate was filtered and washed with water, dried at 110 ° C. overnight and pulverized to obtain 18.6 g of a white powder. As a result of fluorescent X-ray analysis, this white powder was Ca / Si = 0.78, and X-ray diffraction was amorphous.
[0014]
Example 3 Ca / Si = 2/3 = 0.67
400 mL of water was put into a 1 L beaker, and 11.1 g of calcium chloride anhydride was dissolved. In another 200 mL beaker, 31.1 g of No. 3 water glass (SiO ₂ 29%, Na ₂ O 9.4%) was added, and 75 mL of water was added to make a diluted solution. This solution was stirred into the above calcium chloride solution, It poured in in 10 minutes, and also 14.1 g of 30% -NaOH aqueous solution was added similarly.
After pouring, the mixture was stirred for 30 minutes, and the resulting reaction precipitate was filtered and washed with water, dried at 110 ° C. overnight and pulverized to obtain 16.4 g of a white powder. As a result of fluorescent X-ray analysis, this white powder was Ca / Si = 0.65, and X-ray diffraction was amorphous.
[0015]
Example 4 Ca / Si = 1/3 = 0.33
400 mL of water was put into a 1 L beaker, and 7.4 g of anhydrous calcium chloride was dissolved. In another 200 mL beaker, 41.5 g of No. 3 water glass (SiO ₂ 29%, Na ₂ O 9.4%) was added, and 100 mL of water was added to make a diluted solution. Then, 1.0 g of 30% -NaOH aqueous solution was added.
After pouring, the mixture was stirred for 30 minutes, and the resulting reaction precipitate was filtered and washed with water, dried at 110 ° C. overnight and pulverized to obtain 17.0 g of a white powder. As a result of fluorescent X-ray analysis, this white powder was Ca / Si = 0.31 and X-ray diffraction was amorphous.
[0016]
Example 5 Ca / Si = 1/10 = 0.1
400 mL of water was put into a 1 L beaker, and 2.8 g of anhydrous calcium chloride was dissolved. In another 300 mL beaker, 51.7 g of No. 3 water glass (SiO ₂ 29%, Na ₂ O 9.4%) was added, and 100 mL of water was added to make a diluted solution. Poured in minutes.
After pouring, the mixture was stirred for 30 minutes, and then 11.1 g of 35% hydrochloric acid was put into a 200 mL beaker, and 100 mL of water was added to prepare a diluted solution, which was poured into the above mixed solution in 10 minutes.
After pouring, the mixture was stirred for 30 minutes, and the resulting reaction precipitate was filtered and washed with water, dried at 110 ° C. overnight and pulverized to obtain 16.8 g of a white powder. As a result of fluorescent X-ray analysis, this white powder was Ca / Si = 0.097, and X-ray diffraction was amorphous.
[0017]
Example 6 Ca / Si = 1/40 = 0.025
400 mL of water was put into a 1 L beaker, and 0.7 g of calcium chloride anhydride was dissolved. In another 300 mL beaker, 51.7 g of No. 3 water glass (SiO ₂ 29%, Na ₂ O 9.4%) was added, and 100 mL of water was added to make a diluted solution. Poured in minutes.
After pouring, the mixture was stirred for 30 minutes, and then 15.0 g of 35% hydrochloric acid was put into a 200 mL beaker, and 100 mL of water was added to prepare a diluted solution, which was poured into the above mixed solution in 10 minutes.
After pouring, the mixture was stirred for 30 minutes, and the resulting reaction precipitate was filtered and washed with water, dried at 110 ° C. overnight and pulverized to obtain 15.5 g of a white powder. As a result of fluorescent X-ray analysis, this white powder was Ca / Si = 0.024, and X-ray diffraction was amorphous.
[0018]
<Strontium-based>
Example 7 Sr / Si = 1/1 = 1.0
400 mL of water was put into a 1 L beaker, and 24.8 g of anhydrous strontium chloride was dissolved. In another 200 mL beaker, 32.4 g of No. 3 water glass (SiO ₂ 29%, Na ₂ O 9.4%) was added, and 75 mL of water was added to make a diluted solution. This solution was stirred into the above strontium chloride solution, It poured in in 10 minutes, and also 28.7 g of 30% -NaOH aqueous solution was added similarly.
After pouring, the mixture was stirred for 30 minutes, and the resulting reaction precipitate was filtered and washed with water, dried at 110 ° C. overnight and pulverized to obtain 28.4 g of a white powder. As a result of fluorescent X-ray analysis, this white powder was Sr / Si = 0.98, and X-ray diffraction was amorphous.
[0019]
Example 8 Sr / Si = 4/5 = 0.8
400 mL of water was put into a 1 L beaker, and 19.8 g of strontium chloride anhydride was dissolved. In another 200 mL beaker, 32.4 g of No. 3 water glass (SiO ₂ 29%, Na ₂ O 9.4%) was added, and 75 mL of water was added to make a diluted solution. This solution was stirred into the above strontium chloride solution, It poured in in 10 minutes, and also 20.3g of 30% -NaOH aqueous solution was added similarly.
After pouring, the mixture was stirred for 30 minutes, and the resulting reaction precipitate was filtered and washed with water, dried at 110 ° C. overnight and pulverized to obtain 24.6 g of a white powder. As a result of fluorescent X-ray analysis, this white powder was Sr / Si = 0.79, and X-ray diffraction was amorphous.
[0020]
Example 9 Sr / Si = 2/3 = 0.67
400 mL of water was put into a 1 L beaker, and 15.9 g of anhydrous strontium chloride was dissolved. In another 200 mL beaker, 31.1 g of No. 3 water glass (SiO ₂ 29%, Na ₂ O 9.4%) was added, and 75 mL of water was added to make a diluted solution. This solution was stirred into the above strontium chloride solution, It poured in in 10 minutes, and also 14.1 g of 30% -NaOH aqueous solution was added similarly.
After pouring, the mixture was stirred for 30 minutes, and the resulting reaction precipitate was filtered and washed with water, dried at 110 ° C. overnight and pulverized to obtain 21.2 g of a white powder. As a result of fluorescent X-ray analysis, this white powder was Sr / Si = 0.65, and X-ray diffraction was amorphous.
[0021]
Example 10 Sr / Si = 1/3 = 0.33
400 mL of water was put into a 1 L beaker, and 10.6 g of anhydrous strontium chloride was dissolved. In another 200 mL beaker, 41.5 g of No. 3 water glass (SiO ₂ 29%, Na ₂ O 9.4%) was added, and 100 mL of water was added to make a diluted solution. This solution was stirred into the above strontium chloride solution, It poured in in 10 minutes, and also added 1.0 g of 30% -NaOH aqueous solution.
After pouring, the mixture was stirred for 30 minutes, and the resulting reaction precipitate was filtered and washed with water, dried at 110 ° C. overnight and pulverized to obtain 20.1 g of a white powder. As a result of fluorescent X-ray analysis, this white powder was Sr / Si = 0.32 and X-ray diffraction was amorphous.
[0022]
Example 11 Sr / Si = 1/10 = 0.1
400 mL of water was put into a 1 L beaker, and 2.8 g of strontium chloride anhydride was dissolved. In another 300 mL beaker, 51.7 g of No. 3 water glass (SiO ₂ 29%, Na ₂ O 9.4%) was added, and 100 mL of water was added to make a diluted solution. This solution was stirred into the above strontium chloride solution, Poured in 10 minutes.
After pouring, the mixture was stirred for 30 minutes, and then 11.1 g of 35% hydrochloric acid was put into a 200 mL beaker, and 100 mL of water was added to prepare a diluted solution, which was poured into the above mixed solution in 10 minutes.
After pouring, the mixture was stirred for 30 minutes, and the resulting reaction precipitate was filtered and washed with water, dried at 110 ° C. overnight and pulverized to obtain 18.1 g of a white powder. As a result of fluorescent X-ray analysis, this white powder was Sr / Si = 0.098, and X-ray diffraction was amorphous.
[0023]
Example 12 Sr / Si = 1/40 = 0.025
400 mL of water was put into a 1 L beaker and 1.0 g of anhydrous strontium chloride was dissolved. In another 300 mL beaker, 51.7 g of No. 3 water glass (SiO ₂ 29%, Na ₂ O 9.4%) was added, and 100 mL of water was added to make a diluted solution. This solution was stirred into the above strontium chloride solution, Poured in 10 minutes.
After pouring, the mixture was stirred for 30 minutes, and then 15.0 g of 35% hydrochloric acid was put into a 200 mL beaker, and 100 mL of water was added to prepare a diluted solution, which was poured into the above mixed solution in 10 minutes.
After pouring, the mixture was stirred for 30 minutes, and the resulting reaction precipitate was filtered and washed with water, dried at 110 ° C. overnight and pulverized to obtain 15.8 g of white powder. As a result of fluorescent X-ray analysis, this white powder was Sr / Si = 0.023, and X-ray diffraction was amorphous.
[0024]
<Barium-based>
Example 13 Ba / Si = 1/1 = 1.0
400 mL of water was put into a 1 L beaker, and 32.6 g of barium chloride anhydride was dissolved. In another 200 mL beaker, 32.4 g of No. 3 water glass (SiO ₂ 29%, Na ₂ O 9.4%) was added, and 75 mL of water was added to prepare a diluted solution. Then, 28.7 g of 30% -NaOH aqueous solution was added in the same manner.
After pouring, the mixture was stirred for 30 minutes, and the resulting reaction precipitate was filtered and washed with water, dried at 110 ° C. overnight and pulverized to obtain 36.3 g of a white powder. As a result of fluorescent X-ray analysis, this white powder was Ba / Si = 0.97, and the X-ray diffraction was amorphous.
[0025]
Example 14 Ba / Si = 4/5 = 0.8
400 mL of water was put into a 1 L beaker, and 26.1 g of barium chloride anhydride was dissolved. In another 200 mL beaker, 32.4 g of No. 3 water glass (SiO ₂ 29%, Na ₂ O 9.4%) was added, and 75 mL of water was added to prepare a diluted solution. Then, 20.3 g of 30% -NaOH aqueous solution was added in the same manner.
After pouring, the mixture was stirred for 30 minutes, and the resulting reaction precipitate was filtered and washed with water, dried at 110 ° C. overnight, and pulverized to obtain 30.9 g of a white powder. As a result of fluorescent X-ray analysis, this white powder was Ba / Si = 0.78, and X-ray diffraction was amorphous.
[0026]
Example 15 Ba / Si = 2/3 = 0.67
400 mL of water was put into a 1 L beaker, and 20.8 g of barium chloride anhydride was dissolved. In another 200 mL beaker, 31.1 g of No. 3 water glass (SiO ₂ 29%, Na ₂ O 9.4%) was added, and 75 mL of water was added to make a diluted solution. This solution was added to the above barium chloride solution with stirring. Then, 14.1 g of 30% -NaOH aqueous solution was added in the same manner.
After pouring, the mixture was stirred for 30 minutes, and the resulting reaction precipitate was filtered and washed with water, dried at 110 ° C. overnight and pulverized to obtain 26.2 g of a white powder. As a result of fluorescent X-ray analysis, this white powder was Ba / Si = 0.64, and X-ray diffraction was amorphous.
[0027]
Example 16 Ba / Si = 1/3 = 0.33
400 mL of water was put into a 1 L beaker, and 13.9 g of barium chloride anhydride was dissolved. In another 200 mL beaker, 41.5 g of No. 3 water glass (SiO ₂ 29%, Na ₂ O 9.4%) was added and diluted with 100 mL of water. Then, 1.0 g of 30% -NaOH aqueous solution was added.
After pouring, the mixture was stirred for 30 minutes, and the resulting reaction precipitate was filtered and washed with water, dried at 110 ° C. overnight and pulverized to obtain 23.4 g of a white powder. As a result of fluorescent X-ray analysis, this white powder was Ba / Si = 0.32. The X-ray diffraction was amorphous.
[0028]
Example 17 Ba / Si = 1/10 = 0.1
400 mL of water was put into a 1 L beaker, and 5.3 g of barium chloride anhydride was dissolved. In another 300 mL beaker, 51.7 g of No. 3 water glass (SiO ₂ 29%, Na ₂ O 9.4%) was added, and 100 mL of water was added to make a diluted solution. This solution was stirred into the above barium chloride solution, Poured in 10 minutes.
After pouring, the mixture was stirred for 30 minutes, and then 11.1 g of 35% hydrochloric acid was put into a 200 mL beaker, and 100 mL of water was added to prepare a diluted solution, which was poured into the above mixed solution in 10 minutes.
After pouring, the mixture was stirred for 30 minutes, and the resulting reaction precipitate was filtered and washed with water, dried at 110 ° C. overnight and pulverized to obtain 19.3 g of a white powder. As a result of fluorescent X-ray analysis, this white powder was Ba / Si = 0.096, and X-ray diffraction was amorphous.
[0029]
Example 18 Ba / Si = 1/40 = 0.025
400 mL of water was put into a 1 L beaker, and 1.1 g of barium chloride anhydride was dissolved. In another 300 mL beaker, 51.7 g of No. 3 water glass (SiO ₂ 29%, Na ₂ O 9.4%) was added, and 100 mL of water was added to make a diluted solution. This solution was stirred into the above barium chloride solution, Poured in 10 minutes.
After pouring, the mixture was stirred for 30 minutes, and then 15.0 g of 35% hydrochloric acid was put into a 200 mL beaker, and 100 mL of water was added to prepare a diluted solution, which was poured into the above mixed solution in 10 minutes.
After pouring, the mixture was stirred for 30 minutes, and the resulting reaction precipitate was filtered, washed with water, dried at 110 ° C. overnight and pulverized to obtain 16.1 g of a white powder. As a result of fluorescent X-ray analysis, this white powder was Ba / Si = 0.023, and X-ray diffraction was amorphous.
[0030]
2. Paint Test Test Example 1: Anti-corrosion test for Mg alloy Using the pigments of the examples and comparative examples (blank and commercially available anti-corrosion pigments), a baking type epoxy resin paint having the composition shown in the following table was prepared, and a coating film was formed. Later, a salt spray test was performed.
[0031]

[0032]
Substrate: Mg alloy AZ31 (Nippon Test Panel)
Coating: Bar coater curing conditions: Baking temperature 210 ° C (material temperature)
Film thickness: 25 μm
Dispersion: Paint conditioner [0033]
Test item: Salt spray test (maximum 5 points)
The test plate prepared by forming a coating film on the coated plate under the above-described coating conditions was left in a salt spray tester maintained at 35 ° C., and 5% sodium chloride aqueous solution was added at 1 kg / It sprayed on the coating film for 40 hours with the pressure of cm < ² >, the corrosion condition was observed, and it evaluated based on the following evaluation criteria. The corrosion situation was evaluated by the area where rust was generated on the flat surface.
In any evaluation, the higher the evaluation score, the better the rust prevention ability.
[0034]
Evaluation standard of rust prevention effect (according to ASTM D610-68 (1970))
Flat surface rust generation area less than 0.1%: 5-point rust generation area 0.1% to less than 1%: 4-point rust generation area 1% to less than 10%: 3-point rust generation area 10% to 33% Less than: 2 points Rust generation area 33% or more: 1 point
Test Example 2: Anti-corrosion test for aluminum material Using the pigments of Examples and Comparative Examples (blanks and commercially available anti-corrosion pigments), a baking type epoxy resin paint having the composition shown in the following table was prepared, and after coating film formation, A yarn rust test was conducted.
[0036]

[0037]
Substrate: JIS H4000 (A2024P) C (made by Nippon Test Panel)
Coating: Bar coater curing conditions: Baking temperature 210 ° C (material temperature)
Film thickness: 20 μm
Dispersion: Paint conditioner [0038]
Test item: Yarn rust test (maximum 5 points)
In a salt spray tester in which a crosscut reaching the surface of the coated plate is put with a cutter knife into the test plate created by forming a coating film on the coated plate under the above coating conditions, and the temperature in the tank is maintained at 35 ° C. After standing and spraying a 5% aqueous solution of sodium chloride on the coating film at a pressure of 1 kg / cm ² for 24 hours, this test plate was washed with water, and then adjusted to a constant temperature and humidity of 40 ° C.-85% humidity. The sample was left in the machine for 1000 hours, the state of occurrence of yarn rust was observed, and evaluation was performed based on the following evaluation criteria. The occurrence of yarn rust was evaluated by the length of yarn rust from the cut part.
[0039]
Length of thread rust less than 5 mm: Length of 5-point thread rust 5 mm or more to less than 8 mm: Length of 4-point thread rust 8 mm or more to less than 11 mm: Length of 3-point thread rust 11 mm or more to less than 14 mm: 2-point thread Rust length 14 mm or more to less than 17 mm: 1 point thread rust length 17 mm or more: 0 point

[0041]

[0042]
Test Example 3: Anti-corrosion test for galvanized steel sheet Using the pigments of the examples and comparative examples (blanks and commercially available anti-corrosion pigments), a baked polyester resin paint having the composition shown in the table below was prepared, and after the coating film was formed A salt spray test was conducted.
[0043]

[0044]
Coating plate: Galvanized steel sheet SGCC (Nippon Test Panel)
Coating: Bar coater curing conditions: Baking temperature 210 ° C (material temperature)
Film thickness: 10 μm
Dispersion: Paint conditioner Test item: Salt spray test (15 points maximum)
[0045]
In a salt spray tester in which a crosscut reaching the surface of the coated plate is put with a cutter knife into the test plate created by forming a coating film on the coated plate under the above coating conditions, and the temperature in the tank is maintained at 35 ° C. The film was allowed to stand and sprayed with a 5% aqueous sodium chloride solution at a pressure of 1 kg / cm ^{2 on} the coating film for 56 days, and rust generation and swelling of the coating film were observed and evaluated based on the following evaluation criteria.
In addition, the corrosion state was evaluated by the swelling area of the flat part and the area where rust was generated, and the corrosion width of the cut part.
In any evaluation, the higher the evaluation score, the better the rust prevention ability.
[0046]
Evaluation standard of rust prevention effect (according to ASTM D610-68 (1970))
───────────────────────────────────
Flat surface rust generation area less than 0.1%: 5-point rust generation area 0.1% to less than 1%: 4-point rust generation area 1% to less than 10%: 3-point rust generation area 10% to 33% Less than: 2 point rust generation area 33% or more: 1 point ────────────────────────────────────
Evaluation criteria for the effect of preventing blisters (according to ASTM D714-59 (1965))
───────────────────────────────────
Flat part 8F or less: 5 points 8M, 6F: 4 points 8MD, 6M, 4F: 3 points 8D, 6MD, 4M, 2F: 2 points 6D, 4MD or more, 2M or more: 1 point cut part, end face corrosion width 0 1 mm: 5-point corrosion width 1-2 mm: 4-point corrosion width 2-3 mm: 3-point corrosion width 3-4 mm: 2-point corrosion width 4-5 mm: 1-point corrosion width 5 mm or more: 0 points ─────── ────────────────────────────
[0047]

[0048]

Claims (4)

A rust preventive pigment comprising powder particles of an amorphous alkaline earth metal silicate coprecipitate having an atomic ratio of M / Si (M is Ca, Sr or Ba) of 0.025 to 1.0. The rust preventive pigment according to claim 1, wherein the atomic ratio is 0.025 to 0.8. The anticorrosion pigment according to claim 1 or 2, wherein the object of anticorrosion is a nonferrous metal or a nonferrous metal plated steel material. The rust preventive pigment according to claim 3, wherein the non-ferrous metal is zinc, magnesium, aluminum or an alloy thereof.