JP5674382B2 - Anti-rust paint - Google Patents

Anti-rust paint Download PDF

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JP5674382B2
JP5674382B2 JP2010185714A JP2010185714A JP5674382B2 JP 5674382 B2 JP5674382 B2 JP 5674382B2 JP 2010185714 A JP2010185714 A JP 2010185714A JP 2010185714 A JP2010185714 A JP 2010185714A JP 5674382 B2 JP5674382 B2 JP 5674382B2
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加藤　圭一
圭一 加藤
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Kikusui Kagaku Kogyo KK
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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
    • C09D5/08—Anti-corrosive paints
    • C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
    • C09D5/084—Inorganic compounds

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Description

本発明は、建築物や土木構造物等に用いられる鋼材等の金属の錆の発生を防止する防錆塗料に関するものである。   The present invention relates to a rust preventive paint for preventing the occurrence of rust of metals such as steel materials used in buildings and civil engineering structures.

従来、建築物や土木構造物等に用いられる鋼材の錆の発生を防止する防錆塗料には、鉛、錫、亜鉛等の遷移金属やそれらの塩が用いられてきた。しかし、これらの遷移金属及びそれらの塩は経年により防錆塗膜が劣化することにより環境中に流出し、環境汚染を引き起こすおそれがあった。加えて、従来の防錆塗料はそのほとんどがシンナーを希釈剤とする溶剤塗料であったため、揮発した溶剤が大気中へ放出されることが大気汚染の原因の一となっていた。   Conventionally, transition metals such as lead, tin, and zinc and salts thereof have been used in rust preventive coatings that prevent the occurrence of rust in steel materials used in buildings and civil engineering structures. However, these transition metals and their salts may flow out into the environment due to deterioration of the rust-preventing coating film over time, and may cause environmental pollution. In addition, since most of the conventional rust preventive paints are solvent paints using thinner as a diluent, the volatilized solvent is released into the atmosphere, which is one cause of air pollution.

これらの問題を解決するために、水性の環境対応型防錆塗料が提案されている。例えば、カルシウム成分とりん成分とからなり、かつその両成分中のカルシウムとりんとの原子比率（Ｃａ／Ｐ＝ｍ）が０．５０＜ｍ＜１．００である単一物又は混合物を、１８０〜３５０℃で焼成してなる縮合りん酸カルシウムを含み、重金属を含まない無公害防錆顔料と、油性系又はアルキド樹脂系バインダーとを混合して得られることを特徴とする防錆性能及び貯蔵安定性に優れた防錆塗料組成物がある。（例えば、特許文献１参照。）。
また、トリポリリン酸二水素アルミニウムと酸化亜鉛とカルシウム酸化物とを重量基準で全体を１００として５０〜８０／１５〜４５／２〜１０で配合した防錆顔料組成物がある。（例えば、特許文献２参照。）。 In order to solve these problems, water-based environment-friendly rust preventive paints have been proposed. For example, a single substance or a mixture composed of a calcium component and a phosphorus component and having an atomic ratio (Ca / P = m) of calcium and phosphorus in both components of 0.50 <m <1.00 is 180. Rust prevention performance and storage characterized by being obtained by mixing a pollution-free rust preventive pigment containing condensed calcium phosphate baked at ˜350 ° C. and containing no heavy metals, and an oil-based or alkyd resin-based binder There is a rust preventive coating composition having excellent stability. (For example, refer to Patent Document 1).
Moreover, there exists a rust preventive pigment composition which mix | blended 50-80 / 15-45 / 2-10 by making tripoly aluminum dihydrogen phosphate, a zinc oxide, and a calcium oxide into 100 as a whole on a weight basis. (For example, refer to Patent Document 2).

さらに、（Ａ）水酸基含有塗膜形成性樹脂、（Ｂ）架橋剤及び（Ｃ）防錆顔料混合物を含有する塗料組成物であって、該樹脂（Ａ）及び該架橋剤（Ｂ）の合計固形分１００質量部に対して、該防錆顔料混合物（Ｃ）が、（１）五酸化バナジウム、バナジン酸カルシウム及びメタバナジン酸アンモニウムのうちの少なくとも１種３〜５０質量部、（２）カルシウム化合物３〜５０質量部及び（３）金属塩の金属がＺｎ、Ａｌ又はＭｇであるリン酸系金属塩３〜５０質量部、からなり、かつ該防錆顔料混合物（Ｃ）の量が１０〜１５０質量部である耐食性に優れた塗料組成物がある。（例えば、特許文献３参照。）。 Furthermore, it is a coating composition containing (A) a hydroxyl group-containing coating film-forming resin, (B) a crosslinking agent and (C) a rust preventive pigment mixture, and is the total of the resin (A) and the crosslinking agent (B) With respect to 100 parts by mass of the solid content, the rust preventive pigment mixture (C) is (1) at least one of vanadium pentoxide, calcium vanadate and ammonium metavanadate, 3 to 50 parts by mass, and (2) a calcium compound. 3 to 50 parts by mass and (3) 3 to 50 parts by mass of a metal salt of a phosphoric acid metal salt whose metal salt is Zn, Al or Mg, and the amount of the anticorrosive pigment mixture (C) is 10 to 150 There is a coating composition having excellent corrosion resistance, which is part by mass. (For example, refer to Patent Document 3).

特開２００６−１４３８０７号公報（第２〜３頁）JP 2006-143807 A (pages 2 to 3) 特開平７−１３８７７５号公報（第２〜３頁）JP-A-7-138775 (pages 2 and 3) 特開２００８−２２２８３５号公報（第２〜３頁）JP 2008-222835 A (pages 2 to 3)

しかし、これらの防錆塗料組成物は、リン成分や遷移金属を含有しているため、河川湖沼の富栄養化や重金属汚染を引き起こすおそれがあるという問題があった。 However, since these rust-preventive coating compositions contain phosphorus components and transition metals, there is a problem that they may cause eutrophication of rivers and lakes and heavy metal contamination.

解決しようとする問題点は、防錆性に優れ、安全性が高い防錆塗料を提供する点である。   The problem to be solved is to provide a rust-preventing paint that is excellent in rust prevention and has high safety.

請求項１に記載の防錆塗料は、（ａ）水酸化カルシウムと水酸化マグネシウムと、（ｂ）合成樹脂エマルジョンとを含有する防錆塗料であって、
前記防錆塗料に含有される水分の質量を１００質量部に対する前記（ａ）成分の質量が６０〜１４０質量部であり、
前記（ｂ）成分の不揮発分１００質量部に対する前記（ａ）成分の質量が５０〜１５０質量部であることを特徴とする。
なお、ここでいう「不揮発分」とは、ＪＩＳ Ｋ５６０１−１−２（２００８）に準じて測定した「加熱残分」である。測定における試験条件は、加熱時間６０分、温度１２５℃、試料量１±０．２ｇである。
Anticorrosive paint according to claim 1 comprises: (a) calcium hydroxide and magnesium hydroxide, anticorrosive paint containing the (b) a synthetic resin emulsion,
The mass of the component (a) with respect to 100 parts by mass of the moisture contained in the anticorrosive paint is 60 to 140 parts by mass,
The mass of the component (a) is 50 to 150 parts by mass with respect to 100 parts by mass of the nonvolatile content of the component (b).
In addition, the “nonvolatile content” referred to here is a “heating residue” measured according to JIS K5601-1-2 (2008). The test conditions in the measurement are a heating time of 60 minutes, a temperature of 125 ° C., and a sample amount of 1 ± 0.2 g.

請求項２に記載の防錆塗料は、請求項１に記載の防錆塗料が、前記水酸化カルシウムの含有量を１００質量部としたときの水酸化マグネシウムの含有量が３０〜７５質量部であることを特徴とする。
The rust preventive paint according to claim 2 is characterized in that the content of magnesium hydroxide is 30 to 75 parts by mass when the content of calcium hydroxide is 100 parts by mass. It is characterized by being.

請求項３に記載の防錆塗料は、請求項１又は２に記載の防錆塗料が、リン成分、遷移金属、第１２族元素、第１３族元素及びこれらの塩を実質的に含有しないことを特徴とする。
なお、「実質的に含有しない」とは、本発明の作用効果を妨げない限度において、不純物等として微量に含有する場合も含む。
In the rust preventive paint according to claim 3, the rust preventive paint according to claim 1 or 2 is substantially free of a phosphorus component, a transition metal, a group 12 element, a group 13 element and a salt thereof. It is characterized by.
In addition, “substantially not containing” includes the case where it is contained in a trace amount as an impurity or the like as long as the effects of the present invention are not hindered.

請求項４に記載の防錆塗料は、請求項１〜３のいずれかに記載の防錆塗料が、前記（ｂ）合成樹脂エマルジョンのガラス転移点が２５〜−４０℃であることを特徴とする。
The rust preventive paint according to claim 4 is characterized in that the glass transition point of the (b) synthetic resin emulsion is 25 to -40 ° C. To do.

請求項１〜２に記載の発明によれば、防錆性能に優れ、安全性が高い防錆塗料を得られるという利点があることに加え、防錆塗料の貯蔵安定性に優れるという利点がある。
According to the inventions described in claims 1 and 2 , in addition to the advantage that an anticorrosive paint having excellent rust prevention performance and high safety can be obtained, there is an advantage that the storage stability of the anticorrosive paint is excellent. .

請求項３に記載の発明によれば、特に安全性が高い防錆塗料を得られるという利点がある。
According to the invention described in claim 3 , there is an advantage that a rust-proof paint having a particularly high safety can be obtained.

請求項４に記載の発明によれば、第２族元素の水酸化物又は酸化物との混和性に優れるとともに柔軟な塗膜を形成することができ、塗膜に傷がつくことを抑制することができるという利点がある。
According to invention of Claim 4, it is excellent in the miscibility with the hydroxide or oxide of a group 2 element, and a flexible coating film can be formed, and it suppresses that a coating film is damaged. There is an advantage that you can .

以下、本発明を具体化した実施形態を説明する。
本発明の防錆塗料は、リン成分や遷移金属を含まなくても錆の発生を防止することができる防錆塗料である。なお、本発明の防錆塗料をより安全性が高いものとするためには、リン成分、遷移金属、第１２族元素、第１３族元素及びこれらの塩を実質的に含有しないことが好ましい。 Hereinafter, embodiments embodying the present invention will be described.
The rust preventive paint of the present invention is a rust preventive paint capable of preventing the occurrence of rust even without containing a phosphorus component or a transition metal. In order to make the rust preventive paint of the present invention more safe, it is preferable that the phosphorus component, transition metal, Group 12 element, Group 13 element and salts thereof are not substantially contained.

本発明の防錆塗料の組成は例えば以下のようなものである。
組成例：合成樹脂エマルジョンとしてのアクリル樹脂エマルジョン（不揮発分５０質量％）２００質量部、水酸化カルシウム６０質量部、水酸化マグネシウム４０質量部、酸化マグネシウム２質量部、増粘剤１質量部、消泡剤１質量部、水１０質量部。 The composition of the rust preventive paint of the present invention is as follows, for example.
Composition example: 200 mass parts of acrylic resin emulsion (non-volatile content 50 mass%) as synthetic resin emulsion, 60 mass parts of calcium hydroxide, 40 mass parts of magnesium hydroxide, 2 mass parts of magnesium oxide, 1 mass part of thickener, 1 part by mass of foaming agent, 10 parts by mass of water.

前記遷移金属とは、周期表の第３族から第１１族に属する金属元素をいう。   The transition metal refers to a metal element belonging to Group 3 to Group 11 of the periodic table.

前記第１２族元素及び第１３族元素とは、それぞれ周期表の第１２族及び第１３族に属する元素をいう。具体的には亜鉛、カドミウム、水銀、ホウ素、アルミニウム、ガリウム、インジウム、タリウム等をいう。   The Group 12 element and Group 13 element are elements belonging to Group 12 and Group 13 of the periodic table, respectively. Specifically, it means zinc, cadmium, mercury, boron, aluminum, gallium, indium, thallium, and the like.

前記合成樹脂エマルジョンに使用される合成樹脂は、アクリル樹脂に限らず任意に設定することができる。例えば、アクリル樹脂、ポリエステル樹脂、アクリル樹脂、フッ素樹脂、エポキシ樹脂、ポリウレタン樹脂、ポリエーテル樹脂、酢酸ビニル樹脂、シリコーン樹脂等が挙げられる。これらは単独で用いても良いし、２以上を混合して用いても良い。また、これらを構成するモノマーを共重合させて用いても良い。   The synthetic resin used for the synthetic resin emulsion is not limited to the acrylic resin, and can be arbitrarily set. For example, acrylic resin, polyester resin, acrylic resin, fluororesin, epoxy resin, polyurethane resin, polyether resin, vinyl acetate resin, silicone resin, and the like can be given. These may be used singly or in combination of two or more. Moreover, you may use by copolymerizing the monomer which comprises these.

前記合成樹脂エマルジョンの樹脂組成はアクリル樹脂又はシリコーン樹脂およびこれらの共重合樹脂であることが好ましい。合成樹脂エマルジョンの樹脂組成がアクリル樹脂又はシリコーン樹脂およびこれらの共重合樹脂であることにより、塗膜の耐候性に優れる。そのため、例えば、防錆塗膜の保護のために設けた上塗塗膜が剥がれて防錆塗膜が露出した場合、或いは上塗塗膜を設けなかった場合でも防錆塗膜の劣化を抑制することができ、防錆性能を維持することができる。   The resin composition of the synthetic resin emulsion is preferably an acrylic resin or a silicone resin and a copolymer resin thereof. When the resin composition of the synthetic resin emulsion is an acrylic resin, a silicone resin, or a copolymer resin thereof, the weather resistance of the coating film is excellent. Therefore, for example, when the top coating film provided for protection of the rust prevention coating film is peeled off and the rust prevention coating film is exposed, or even when no top coating film is provided, the deterioration of the rust prevention coating film is suppressed. Rust prevention performance can be maintained.

また、前記合成樹脂エマルジョンは樹脂組成中の−ＣＯＯＨ基の含有量を低減することが好ましい。−ＣＯＯＨ基の含有量を低減することにより、水酸化カルシウム、水酸化マグネシウム、酸化マグネシウム、酸化カルシウム等の第２族元素の水酸化物又は酸化物との混和性を向上することができる。   Moreover, it is preferable that the said synthetic resin emulsion reduces content of -COOH group in a resin composition. By reducing the content of —COOH groups, miscibility with hydroxides or oxides of Group 2 elements such as calcium hydroxide, magnesium hydroxide, magnesium oxide, and calcium oxide can be improved.

また、前記合成樹脂エマルジョンのガラス転移点（Ｔｇ）は、好ましくは２５〜−４０℃、より好ましくは１５〜−３０℃、最も好ましくは１０〜−２５℃である。ガラス転移点がこの範囲にあるとき、第２族元素の水酸化物又は酸化物との混和性に優れるとともに柔軟な塗膜を形成することができ、塗膜に傷がつくことを抑制することができる。ガラス転移点が２５℃を超える場合には、塗膜が硬すぎて塗膜表面に外力が加わった場合に傷がつきやすくなる。逆に、ガラス転移点が−４０℃未満の場合には、塗膜が軟らかすぎて塗膜表面に外力が加わった場合に変形してしまうおそれがある。   The glass transition point (Tg) of the synthetic resin emulsion is preferably 25 to -40 ° C, more preferably 15 to -30 ° C, and most preferably 10 to -25 ° C. When the glass transition point is in this range, it is possible to form a flexible coating film with excellent miscibility with the hydroxide or oxide of the Group 2 element, and to prevent the coating film from being damaged. Can do. When the glass transition point exceeds 25 ° C., the coating film is too hard and is easily damaged when an external force is applied to the coating film surface. On the contrary, when the glass transition point is lower than −40 ° C., the coating film is too soft and may be deformed when an external force is applied to the coating film surface.

前記水酸化カルシウム、水酸化マグネシウム、酸化マグネシウム等の第２族元素の水酸化物又は酸化物の少なくとも１以上を用いることによって、防錆性能に優れた防錆塗膜を得ることができる。なお、第２族元素の水酸化物又は酸化物の中でも、水酸化カルシウム、水酸化マグネシウム、酸化マグネシウム、酸化カルシウムの少なくとも１以上を用いることが特に好ましい。これらを用いることにより、防錆性能に優れた防錆塗膜を得ることができる。また、これらは、地殻中に豊富に含まれるため入手が容易であるとともに安全性に優れる。
特に、水酸化カルシウム、水酸化マグネシウム等の第２族元素の水酸化物の少なくとも１以上を含有することで、より防錆性能に優れた防錆塗膜を得ることができる。 By using at least one or more hydroxides or oxides of Group 2 elements such as calcium hydroxide, magnesium hydroxide, and magnesium oxide, a rust-preventing coating film excellent in rust-preventing performance can be obtained. In addition, it is particularly preferable to use at least one of calcium hydroxide, magnesium hydroxide, magnesium oxide, and calcium oxide among the hydroxides or oxides of Group 2 elements. By using these, it is possible to obtain a rust-proof coating film excellent in rust-proof performance. Moreover, since these are contained abundantly in the crust, they are easy to obtain and have excellent safety.
In particular, by containing at least one or more hydroxides of Group 2 elements such as calcium hydroxide and magnesium hydroxide, it is possible to obtain a rust-preventing coating film with more excellent anti-rust performance.

なお、前記合成樹脂エマルジョンの不揮発分１００質量部に対する水酸化カルシウム、水酸化マグネシウム、酸化マグネシウム、酸化カルシウムの合計質量は５０〜１５０質量部であることが好ましく、６０〜１４０質量部であることがより好ましく、７０〜１３０質量部であることが更に好ましく、８５〜１１５質量部であることが最も好ましい。合成樹脂エマルジョンの不揮発分１００質量部に対する水酸化カルシウム、水酸化マグネシウム、酸化マグネシウム、酸化カルシウムの合計質量がこの範囲にあるとき、防錆塗料の貯蔵安定性に優れるとともに、防錆性能に優れる。合成樹脂エマルジョンの不揮発分１００質量部に対する水酸化カルシウム、水酸化マグネシウム、酸化マグネシウム、酸化カルシウムの合計質量が５０質量部未満の場合には、防錆性能が十分でない場合がある。逆に、前記合計質量が１５０質量部を超える場合には、防錆塗料の貯蔵安定性が悪く、防錆塗料を貯蔵した際に塗料が増粘したり、分離したりしてしまう場合がある。
なお、上述した「水酸化カルシウム、水酸化マグネシウム、酸化マグネシウム、酸化カルシウムの合計質量」において、水酸化カルシウム、水酸化マグネシウム、酸化マグネシウム、及び酸化カルシウムのうち１〜３種に質量は０であってもよい。 The total mass of calcium hydroxide, magnesium hydroxide, magnesium oxide, and calcium oxide is preferably 50 to 150 parts by mass and preferably 60 to 140 parts by mass with respect to 100 parts by mass of the nonvolatile content of the synthetic resin emulsion. More preferably, it is 70-130 mass parts, More preferably, it is 85-115 mass parts. When the total mass of calcium hydroxide, magnesium hydroxide, magnesium oxide and calcium oxide with respect to 100 parts by mass of the nonvolatile content of the synthetic resin emulsion is in this range, the storage stability of the anticorrosive paint is excellent and the antirust performance is excellent. When the total mass of calcium hydroxide, magnesium hydroxide, magnesium oxide and calcium oxide with respect to 100 parts by mass of the nonvolatile content of the synthetic resin emulsion is less than 50 parts by mass, the rust prevention performance may not be sufficient. On the contrary, when the total mass exceeds 150 parts by mass, the storage stability of the rust preventive paint is poor, and the paint may thicken or separate when the rust preventive paint is stored. .
In the above-mentioned “total mass of calcium hydroxide, magnesium hydroxide, magnesium oxide, and calcium oxide”, 1 to 3 types of calcium hydroxide, magnesium hydroxide, magnesium oxide, and calcium oxide had a mass of 0. May be.

また、前記水酸化カルシウムと水酸化マグネシウムとの合計質量１００質量部に対する酸化マグネシウムと酸化カルシウムとの合計質量は好ましくは１５質量部以下、より好ましくは７質量部以下、最も好ましくは５質量部以下である。前記水酸化カルシウムと水酸化マグネシウムとの合計質量１００質量部に対する酸化マグネシウムと酸化カルシウムとの合計質量がこの範囲にあるとき、防錆性能に優れるとともに、防錆塗料の貯蔵安定性に優れる。水酸化カルシウムと水酸化マグネシウムとの合計質量１００質量部に対する酸化マグネシウムと酸化カルシウムとの合計質量が１５質量部を超える場合には、防錆塗料の貯蔵安定性がよくない場合がある。   The total mass of magnesium oxide and calcium oxide with respect to 100 mass parts of the total mass of calcium hydroxide and magnesium hydroxide is preferably 15 mass parts or less, more preferably 7 mass parts or less, and most preferably 5 mass parts or less. It is. When the total mass of magnesium oxide and calcium oxide with respect to 100 parts by mass of the total mass of calcium hydroxide and magnesium hydroxide is in this range, the rust prevention performance is excellent and the storage stability of the rust prevention paint is excellent. When the total mass of magnesium oxide and calcium oxide with respect to 100 parts by mass of the total mass of calcium hydroxide and magnesium hydroxide exceeds 15 parts by mass, the storage stability of the anticorrosive paint may not be good.

なお、前記水酸化カルシウムと水酸化マグネシウムとの合計質量１００質量部に対する酸化マグネシウムの含有量は好ましくは５質量部以下である。 In addition, content of magnesium oxide with respect to 100 mass parts of total mass of the said calcium hydroxide and magnesium hydroxide becomes like this. Preferably it is 5 mass parts or less.

また、前記水酸化カルシウムの含有量を１００質量部としたときの水酸化マグネシウムの含有量は好ましくは３０〜７５質量部であり、より好ましくは４０〜７０質量部であり、最も好ましくは４５〜６０質量部である。水酸化カルシウムの含有量を１００質量部としたときの水酸化マグネシウムの含有量がこの範囲にあるとき、防錆性能に優れるとともに、防錆塗料の貯蔵安定性に優れる。水酸化カルシウムの含有量を１００質量部としたときの水酸化マグネシウムの含有量が４０質量部未満の場合には、防錆塗料中の水酸化カルシウムの質量が相対的に増加するため、防錆塗料の貯蔵安定性が十分でない。逆に、含有量が７０質量部を超える場合には防錆性能が十分でない。   Further, the content of magnesium hydroxide when the content of calcium hydroxide is 100 parts by mass is preferably 30 to 75 parts by mass, more preferably 40 to 70 parts by mass, and most preferably 45 to 45 parts by mass. 60 parts by mass. When the content of magnesium hydroxide when the content of calcium hydroxide is 100 parts by mass is in this range, the rust prevention performance is excellent and the storage stability of the rust prevention paint is excellent. When the content of magnesium hydroxide is less than 40 parts by mass when the content of calcium hydroxide is 100 parts by mass, the mass of calcium hydroxide in the anticorrosive paint relatively increases. The storage stability of the paint is not sufficient. Conversely, when the content exceeds 70 parts by mass, the rust prevention performance is not sufficient.

前記水酸化カルシウム、水酸化マグネシウム、酸化マグネシウム、酸化カルシウムは単独で用いても良いし、これらが混合したものを用いても良い。これらが混合されたものとしては、例えば、ブルース石、消石灰、ドロマイトプラスター等が挙げられる。   The said calcium hydroxide, magnesium hydroxide, magnesium oxide, and calcium oxide may be used independently, and what mixed these may be used. As a mixture of these, for example, bluestone, slaked lime, dolomite plaster and the like can be mentioned.

本発明の防錆塗料は、例えば、水性塗料とすることができる。
前記防錆塗料に含有される水分の質量（前記合成樹脂エマルジョンに含有されている水分と塗料製造の際に添加される水分との合計質量）を１００質量部とした場合の水酸化カルシウム、水酸化マグネシウム、酸化マグネシウム、酸化カルシウムの合計質量は好ましくは６０〜１４０質量部であり、より好ましくは７０〜１２０質量部であり、最も好ましくは９０〜１１０質量部である。防錆塗料に含有される水分の質量を１００質量部とした場合の水酸化カルシウム、水酸化マグネシウム、酸化マグネシウム、酸化カルシウムの合計質量がこの範囲にあるとき、防錆性能に優れるとともに防錆塗料の貯蔵安定性に優れる。防錆塗料に含有される水分の質量を１００質量部とした場合の水酸化カルシウム、水酸化マグネシウム、酸化マグネシウム、酸化カルシウムの合計質量が３０質量部未満の場合には、防錆塗料中の水分が多くなるため乾燥性が十分でなく、塗料の体積減少によって塗膜の収縮が大きくなるため、ひび割れが生ずるおそれがある。逆に、合計質量が７０質量部を超える場合には、防錆塗料の貯蔵安定性が十分でない。 The anticorrosive paint of the present invention can be, for example, an aqueous paint.
Calcium hydroxide, water when the mass of water contained in the anticorrosive paint (the total mass of the water contained in the synthetic resin emulsion and the water added during the production of the paint) is 100 parts by mass The total mass of magnesium oxide, magnesium oxide and calcium oxide is preferably 60 to 140 parts by mass, more preferably 70 to 120 parts by mass, and most preferably 90 to 110 parts by mass. When the total mass of calcium hydroxide, magnesium hydroxide, magnesium oxide, and calcium oxide in this range is 100 parts by mass of moisture contained in the rust-proof paint, the rust-proof paint has excellent rust-proof performance. Excellent storage stability. When the total mass of calcium hydroxide, magnesium hydroxide, magnesium oxide, and calcium oxide is less than 30 parts by mass when the mass of moisture contained in the rust-proof coating is 100 parts by mass, the moisture in the rust-proof coating Therefore, the drying property is not sufficient, and the shrinkage of the coating film increases due to the decrease in the volume of the paint, which may cause cracks. Conversely, when the total mass exceeds 70 parts by mass, the storage stability of the anticorrosive paint is not sufficient.

前記防錆塗料の組成中には、本発明の効果を損なわない限りにおいて、必要に応じて通常の塗料用添加剤を使用することができる。例えば、増粘剤、分散剤、消泡剤、造膜助剤、湿潤剤、凍結防止剤、着色顔料、体質顔料、架橋剤、金属膜、紫外線吸収剤、酸化防止剤、レベリング剤、シランカップリング剤等が挙げられる。   In the composition of the anticorrosive paint, usual paint additives can be used as necessary as long as the effects of the present invention are not impaired. For example, thickeners, dispersants, antifoaming agents, film-forming aids, wetting agents, antifreeze agents, colored pigments, extender pigments, cross-linking agents, metal films, UV absorbers, antioxidants, leveling agents, silane cups A ring agent etc. are mentioned.

前記増粘剤としては、メチルセルロース、カルボキシメチルセルロース、ヒドロキシエチルセルロース、ポリビニルアルコール、ポリアクリル酸ナトリウム等のセメント、モルタル等の混和に用いられるものが好ましい。   As the thickener, those used for mixing cement such as methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, polyvinyl alcohol, sodium polyacrylate, and mortar are preferable.

以上のように構成された防錆塗料は、例えば以下のようにして使用される。基材としての３００ｍｍ×３００×１０ｍｍ×１５ｍｍのＨ形鋼材にスプレーで、乾燥後の塗膜の厚さが２５０μｍとなるように塗装し、常温で１６時間乾燥させた後、上塗塗料としてのアクリルシリコーン樹脂塗料をスプレーにより乾燥後の塗膜の厚さ７５μｍとなるように塗装して５時間乾燥させる。   The anticorrosion paint constituted as described above is used as follows, for example. After spraying on a 300 mm x 300 x 10 mm x 15 mm H-shaped steel material as a base material, the coating film thickness after drying is 250 μm, drying at room temperature for 16 hours, and then acrylic as a top coat. The silicone resin paint is applied by spraying so that the thickness of the dried coating film becomes 75 μm and dried for 5 hours.

前記基材はＨ形鋼材に限らず任意に設定することができる。例えば、角形鋼材、丸形鋼材、Ｌ形鋼材、線鋼材、鋼板等が挙げられる。また、鉄鋼に限らず、アルミニウム等の他の金属でも良く、ステンレス、トタン等の合金でも良い。基材は、金属又は合金であれば、その用途、形状等は特に限定されない。   The base material is not limited to the H-shaped steel material and can be arbitrarily set. For example, a square steel material, a round steel material, an L-shaped steel material, a wire steel material, a steel plate, etc. are mentioned. In addition to steel, other metals such as aluminum may be used, and alloys such as stainless steel and tin may be used. If a base material is a metal or an alloy, the use, shape, etc. will not be specifically limited.

前記防錆塗料は基材に直接塗装しても良いし、亜鉛めっき、溶融亜鉛めっき等のめっき処理をした後に塗装しても良い。また、基材の表面をショットブラスト、ケレン、サンディング等の処理をしてから塗装しても良い。   The anticorrosive paint may be applied directly to the substrate, or may be applied after a plating treatment such as galvanizing or hot dip galvanizing. Further, the surface of the base material may be coated after being treated with shot blasting, keren, sanding or the like.

前記防錆塗料及び上塗塗料の乾燥は自然乾燥に限らず、電熱器やヒーターなどによって環境を高温にして乾燥時間を早める強制乾燥でも良い。また、乾燥時間も条件によって任意に設定することができる。   The drying of the rust preventive paint and the top coat is not limited to natural drying, and may be forced drying in which the environment is heated to high temperature by an electric heater or a heater to shorten the drying time. Further, the drying time can be arbitrarily set depending on the conditions.

前記上塗塗料はアクリルシリコーン樹脂塗料に限らず、通常の塗装に用いられる塗料を任意に設定することができる。また、防錆塗料に用いる合成樹脂エマルジョンの組成がアクリル樹脂又はシリコーン樹脂及びこれらの共重合樹脂である場合には、防錆塗料自体が耐候性に優れているため、上塗塗料を省略することもできる。   The top coating is not limited to the acrylic silicone resin coating, and a coating used for normal coating can be arbitrarily set. In addition, when the composition of the synthetic resin emulsion used for the rust preventive paint is an acrylic resin or a silicone resin and a copolymer resin thereof, the rust preventive paint itself is excellent in weather resistance, so the top coat may be omitted. it can.

なお、前記防錆塗料の塗装厚みは、乾燥後の塗膜の厚みが好ましくは５０〜５０００μｍであり、より好ましくは８０〜１０００μｍであり、特に好ましくは１００〜５００μｍである。乾燥後の塗膜の厚みがこの範囲にあるとき、防錆性に優れた防錆塗膜を得ることができる。塗膜の厚みが薄すぎる場合には十分な防錆性をもつ塗膜が得られない場合がある。逆に、塗膜の厚みが厚すぎると、十分な防錆性は得られるものの塗膜の重量が大きくなり、塗装された基材の重量が大きくなってしまうため、厚い塗膜を形成することは好ましくない。塗膜の厚みが５０００μｍ以下でも十分な防錆性は得られるので、塗膜の厚みは５０００μｍ以下であることが好ましい。   In addition, as for the coating thickness of the said rust preventive paint, the thickness of the coating film after drying becomes like this. Preferably it is 50-5000 micrometers, More preferably, it is 80-1000 micrometers, Especially preferably, it is 100-500 micrometers. When the thickness of the coating film after drying is in this range, a rust-preventing coating film excellent in rust-preventing property can be obtained. When the thickness of the coating film is too thin, a coating film having sufficient rust prevention properties may not be obtained. Conversely, if the thickness of the coating film is too thick, sufficient rust prevention can be obtained, but the coating film weight increases and the coated substrate weight increases, so a thick coating film must be formed. Is not preferred. Since sufficient antirust property is obtained even if the thickness of the coating film is 5000 μm or less, the thickness of the coating film is preferably 5000 μm or less.

また、前記上塗塗料の塗装厚みは、使用する上塗塗料に応じて適宜設定すればよい。   Moreover, what is necessary is just to set the coating thickness of the said top coat suitably according to the top coat used.

前記防錆塗料及び上塗塗料の施工はスプレーに限らず、通常の塗装に用いるものであれば任意に設定することができる。例えば、刷毛、スプレー、ロールコーター、フローコーター等の塗装機、ハケ、多孔質ローラー、ウールローラー、鏝等が挙げられる。 The construction of the rust preventive paint and the top coat is not limited to spraying, but can be arbitrarily set as long as it is used for normal painting. Examples thereof include brushes, sprayers, roll coaters, flow coater and other coating machines, brushes, porous rollers, wool rollers, wrinkles and the like.

本実施形態は以下に示す効果を発揮することができる。
・前記合成樹脂エマルジョンの樹脂組成中の−ＣＯＯＨ基の含有量を低減することにより、水酸化カルシウム、水酸化マグネシウム、酸化マグネシウム、酸化カルシウム等の第２族元素の水酸化物又は酸化物との混和性を向上することができる。 This embodiment can exhibit the following effects.
-By reducing the content of -COOH groups in the resin composition of the synthetic resin emulsion, with the hydroxide or oxide of Group 2 elements such as calcium hydroxide, magnesium hydroxide, magnesium oxide, calcium oxide, etc. Miscibility can be improved.

・前記合成樹脂エマルジョンのガラス転移点が２５〜−４０℃であることにより、第２族元素の水酸化物又は酸化物との混和性に優れるとともに柔軟な塗膜を形成することができ、塗膜に傷がつくことを抑制することができる。   -When the glass transition point of the synthetic resin emulsion is 25 to -40 ° C, it is excellent in miscibility with the hydroxide or oxide of the Group 2 element and can form a flexible coating film. The film can be prevented from being damaged.

・水酸化カルシウム、水酸化マグネシウム、酸化マグネシウム、酸化カルシウムから選択される少なくとも１以上を用いることにより、防錆性能に優れた防錆塗膜を得ることができる。また、これらは地殻中に豊富に含まれるため入手が容易であるとともに安全性に優れる。   -By using at least 1 or more selected from calcium hydroxide, magnesium hydroxide, magnesium oxide, and calcium oxide, a rust-proof coating film excellent in rust-proof performance can be obtained. Moreover, since these are abundantly contained in the crust, they are easy to obtain and have excellent safety.

・前記合成樹脂エマルジョンの不揮発分１００質量部に対する水酸化カルシウム、水酸化マグネシウム、酸化マグネシウム、酸化カルシウムの合計質量が５０〜１５０質量部であることにより、防錆塗料の貯蔵安定性に優れるとともに防錆性能に優れる。   -The total mass of calcium hydroxide, magnesium hydroxide, magnesium oxide, and calcium oxide with respect to 100 parts by mass of the nonvolatile content of the synthetic resin emulsion is 50 to 150 parts by mass, so that the storage stability of the anticorrosive paint is excellent and is prevented. Excellent rust performance.

・前記第水酸化カルシウムと水酸化マグネシウムとの合計質量１００質量部に対する酸化マグネシウムと酸化カルシウムとの合計質量が１５質量部であることにより、防錆性能に優れるとともに、防錆塗料の貯蔵安定性に優れる。   -The total mass of magnesium oxide and calcium oxide with respect to 100 mass parts of the total mass of the calcium hydroxide and magnesium hydroxide is 15 mass parts, so that the rust prevention performance is excellent and the storage stability of the rust prevention paint Excellent.

・前記水酸化カルシウムの含有量を１００質量部としたときの水酸化マグネシウムの含有量が３０〜７５質量部であることにより、防錆性能に優れるとともに、防錆塗料の貯蔵安定性に優れる。   -When the content of magnesium hydroxide is 30 to 75 parts by mass when the content of calcium hydroxide is 100 parts by mass, the antirust performance is excellent and the storage stability of the anticorrosive paint is excellent.

・前記防錆塗料に含有される水分の質量を１００質量部とした場合の水酸化カルシウム、水酸化マグネシウム、酸化マグネシウム、酸化カルシウムの合計質量が６０〜１４０質量部であることにより、防錆性能に優れるとともに防錆塗料の貯蔵安定性に優れる。
なお、本発明の前記実施形態を次のように変更して構成することもできる。 -When the total mass of calcium hydroxide, magnesium hydroxide, magnesium oxide, and calcium oxide is 60 to 140 parts by mass when the mass of moisture contained in the anticorrosive coating is 100 parts by mass, the antirust performance In addition to excellent storage stability of anticorrosive paints.
In addition, the said embodiment of this invention can also be changed and comprised as follows.

・前記実施形態においては、新しい鋼材に直接塗装したが、錆が発生した鋼材に直接塗装しても良い。また、錆をケレンしてから塗装しても良い。 -In the said embodiment, although it painted directly on the new steel material, you may paint directly on the steel material in which rust generate | occur | produced. Also, the paint may be applied after cleansing the rust.

以下、前記実施形態を具体化した実施例及び比較例について説明する。
試験はＪＩＳ Ｋ ５０５１：２００８（構造物用さび止めペイント）の７．１６（サイクル腐食性）に準拠して行った。ただし、防錆塗料の塗装は１回塗りとし、乾燥塗膜の厚さは１００μｍとした。また、貯蔵安定性を確認するため、防錆塗料２５０ｇをプラスチック容器に収容し、５０℃で２週間放置して塗料の状態を確認した。 Hereinafter, examples and comparative examples embodying the embodiment will be described.
The test was conducted in accordance with 7.16 (cycle corrosion) of JIS K 5051: 2008 (rust preventive paint for structures). However, the anti-corrosion paint was applied once and the thickness of the dry coating film was 100 μm. In order to check the storage stability, 250 g of the rust preventive paint was placed in a plastic container and left at 50 ° C. for 2 weeks to check the state of the paint.

（実施例１）
実施例１の防錆塗料の組成は合成樹脂エマルジョンとしてのアクリルシリコーン共重合樹脂エマルジョン（不揮発分５６質量％、ガラス転移点−１５℃）１２０質量部、水酸化カルシウム４０質量部、水酸化マグネシウム２０質量部、増粘剤１質量部、消泡剤１質量部、水１０質量部である。
使用した増粘剤はセルロース系増粘剤（メチルセルロース）である。また、使用した消泡剤はシリコーン系消泡剤である。なお、増粘剤、消泡剤は、後述する実施例２〜１４、比較例１〜４でも同様のものを使用した。
試験の結果、１２０サイクル後の試験体は３枚ともに塗膜に錆、膨れ、割れ及び剥がれは認められなかった。また、貯蔵安定性に問題は見られなかった。 Example 1
The composition of the anticorrosive paint of Example 1 is 120 parts by mass of an acrylic silicone copolymer resin emulsion (non-volatile content 56% by mass, glass transition point -15 ° C) as a synthetic resin emulsion, 40 parts by mass of calcium hydroxide, magnesium hydroxide 20 They are 1 part by mass, 1 part by mass of a thickener, 1 part by mass of an antifoaming agent, and 10 parts by mass of water.
The thickener used is a cellulosic thickener (methylcellulose). Moreover, the used antifoamer is a silicone type antifoamer. The same thickener and antifoaming agent were used in Examples 2 to 14 and Comparative Examples 1 to 4 described later.
As a result of the test, no rust, blistering, cracking and peeling were observed in the three coatings after 120 cycles. In addition, no problem was found in storage stability.

（実施例２）
実施例２の防錆塗料の組成は合成樹脂エマルジョンとしてのアクリル樹脂エマルジョン（不揮発分５０質量％、ガラス転移点８℃）１２０質量部、水酸化カルシウム４０質量部、水酸化マグネシウム２０質量部、増粘剤１質量部、消泡剤１質量部である。
試験の結果、１２０サイクル後の試験体は３枚ともに塗膜に錆、膨れ、割れ及び剥がれは認められなかった。また、貯蔵安定性に問題は見られなかった。 (Example 2)
The composition of the anticorrosive paint of Example 2 is 120 parts by mass of an acrylic resin emulsion (nonvolatile content 50% by mass, glass transition point 8 ° C.) as a synthetic resin emulsion, 40 parts by mass of calcium hydroxide, 20 parts by mass of magnesium hydroxide, and increased. 1 part by mass of a sticking agent and 1 part by mass of an antifoaming agent.
As a result of the test, no rust, blistering, cracking and peeling were observed in the three coatings after 120 cycles. In addition, no problem was found in storage stability.

（実施例３）
実施例３の防錆塗料の組成は合成樹脂エマルジョンとしてのアクリル樹脂エマルジョン（不揮発分５０質量％、ガラス転移点８℃）１２０質量部、水酸化カルシウム４０質量部、水酸化マグネシウム２０質量部、酸化マグネシウム２質量部、増粘剤１質量部、消泡剤１質量部である。
試験の結果、１２０サイクル後の試験体は３枚ともに塗膜に錆、膨れ、割れ及び剥がれは認められなかった。また、貯蔵安定性に問題は見られなかった。 Example 3
The composition of the anticorrosive paint of Example 3 is 120 parts by mass of an acrylic resin emulsion (nonvolatile content 50% by mass, glass transition point 8 ° C.) as a synthetic resin emulsion, 40 parts by mass of calcium hydroxide, 20 parts by mass of magnesium hydroxide, oxidation 2 parts by mass of magnesium, 1 part by mass of a thickener, and 1 part by mass of an antifoaming agent.
As a result of the test, no rust, blistering, cracking and peeling were observed in the three coatings after 120 cycles. In addition, no problem was found in storage stability.

（参考例４）
参考例４の防錆塗料の組成は合成樹脂エマルジョンとしてのアクリル樹脂エマルジョン（不揮発分５０質量％、ガラス転移点８℃）１２０質量部、水酸化カルシウム６０質量部、増粘剤１質量部、消泡剤１質量部である。
試験の結果、１２０サイクル後の試験体は３枚中２枚に塗膜に錆、膨れ、割れ及び剥がれは認められなかった。残り１枚は切り込み傷の周辺にやや錆の発生が見られた。また、貯蔵安定性に問題は見られなかった。
( Reference Example 4)
The composition of the anticorrosive paint of Reference Example 4 is 120 parts by mass of an acrylic resin emulsion (nonvolatile content 50% by mass, glass transition point 8 ° C.) as a synthetic resin emulsion, 60 parts by mass of calcium hydroxide, 1 part by mass of a thickener, 1 part by mass of foaming agent.
As a result of the test, rust, blistering, cracking and peeling were not observed in the coating film on 2 out of 3 specimens after 120 cycles. The remaining one showed some rust around the notch. In addition, no problem was found in storage stability.

（参考例５）
参考例５の防錆塗料の組成は合成樹脂エマルジョンとしてのアクリル樹脂エマルジョン（不揮発分５０質量％、ガラス転移点８℃）１２０質量部、水酸化マグネシウム６０質量部、増粘剤１質量部、消泡剤１質量部である。
試験の結果、１２０サイクル後の試験体は３枚中２枚に塗膜に錆、膨れ、割れ及び剥がれは認められなかった。残り１枚は切り込み傷の周辺にやや錆と膨れの発生が見られた。また、貯蔵安定性に問題は見られなかった。
( Reference Example 5)
The composition of the anticorrosive paint of Reference Example 5 is 120 parts by mass of an acrylic resin emulsion (nonvolatile content 50% by mass, glass transition point 8 ° C.) as a synthetic resin emulsion, 60 parts by mass of magnesium hydroxide, 1 part by mass of a thickener, 1 part by mass of foaming agent.
As a result of the test, rust, blistering, cracking and peeling were not observed in the coating film on 2 out of 3 specimens after 120 cycles. The remaining one showed some rust and blistering around the notch. In addition, no problem was found in storage stability.

（実施例６）
実施例６の防錆塗料の組成は合成樹脂エマルジョンとしてのアクリル樹脂エマルジョン（不揮発分５０質量％、ガラス転移点−１０℃）１２０質量部、水酸化カルシウム２５質量部、水酸化マグネシウム１２質量部、酸化マグネシウム２質量部、増粘剤１質量部、消泡剤１質量部である。
試験の結果、１２０サイクル後の試験体は３枚中２枚で塗膜に錆、膨れ、割れ及び剥がれは認められなかった。残り１枚は切り込み傷の周辺にやや錆の発生が見られた。また、貯蔵安定性に問題は見られなかった。 (Example 6)
The composition of the anticorrosive paint of Example 6 is 120 parts by mass of an acrylic resin emulsion (nonvolatile content 50% by mass, glass transition point -10 ° C) as a synthetic resin emulsion, 25 parts by mass of calcium hydroxide, 12 parts by mass of magnesium hydroxide, 2 parts by mass of magnesium oxide, 1 part by mass of a thickener, and 1 part by mass of an antifoaming agent.
As a result of the test, rust, blistering, cracking and peeling were not observed in the coating film after 2 out of 3 specimens after 120 cycles. The remaining one showed some rust around the notch. In addition, no problem was found in storage stability.

（実施例７）
実施例７の防錆塗料の組成は合成樹脂エマルジョンとしてのスチレンアクリル共重合樹脂エマルジョン（不揮発分５０質量％、ガラス転移点−２８℃）１２０質量部、水酸化カルシウム４０質量部、水酸化マグネシウム２０質量部、増粘剤１質量部、消泡剤１質量部である。
試験の結果、１２０サイクル後の試験体は３枚ともに塗膜に錆、膨れ、割れ及び剥がれは認められなかった。また、貯蔵安定性に問題は見られなかった。 (Example 7)
The composition of the rust preventive coating material of Example 7 is 120 parts by mass of a styrene acrylic copolymer resin emulsion (nonvolatile content 50% by mass, glass transition point -28 ° C.) as a synthetic resin emulsion, 40 parts by mass of calcium hydroxide, 20 mg of magnesium hydroxide. 1 part by mass, 1 part by mass of a thickener, and 1 part by mass of an antifoaming agent.
As a result of the test, no rust, blistering, cracking and peeling were observed in the three coatings after 120 cycles. In addition, no problem was found in storage stability.

（実施例８）
実施例８の防錆塗料の組成は合成樹脂エマルジョンとしてのアクリルシリコーン共重合樹脂エマルジョン（不揮発分５６質量％、ガラス転移点−１５℃）１２０質量部、水酸化カルシウム４５質量部、水酸化マグネシウム１５質量部、増粘剤１質量部、消泡剤１質量部、水１０質量部である。
試験の結果、１２０サイクル後の試験体は３枚ともに塗膜に錆、膨れ、割れ及び剥がれは認められなかった。また、貯蔵安定性に問題は見られなかった。 (Example 8)
The composition of the anticorrosive paint of Example 8 is 120 parts by mass of an acrylic silicone copolymer resin emulsion (non-volatile content 56% by mass, glass transition point -15 ° C) as a synthetic resin emulsion, 45 parts by mass of calcium hydroxide, 15 magnesium hydroxide. They are 1 part by mass, 1 part by mass of a thickener, 1 part by mass of an antifoaming agent, and 10 parts by mass of water.
As a result of the test, no rust, blistering, cracking and peeling were observed in the three coatings after 120 cycles. In addition, no problem was found in storage stability.

（実施例９）
実施例９の防錆塗料の組成は合成樹脂エマルジョンとしてのアクリルシリコーン共重合樹脂エマルジョン（不揮発分５６質量％、ガラス転移点−１５℃）１２０質量部、水酸化カルシウム３５質量部、水酸化マグネシウム２５質量部、増粘剤１質量部、消泡剤１質量部、水１０質量部である。
試験の結果、１２０サイクル後の試験体は３枚ともに塗膜に錆、膨れ、割れ及び剥がれは認められなかった。また、貯蔵安定性に問題は見られなかった。 Example 9
The composition of the anticorrosive paint of Example 9 was 120 parts by mass of an acrylic silicone copolymer resin emulsion (non-volatile content 56 mass%, glass transition point -15 ° C.) as a synthetic resin emulsion, 35 mass parts of calcium hydroxide, 25 magnesium hydroxide. They are 1 part by mass, 1 part by mass of a thickener, 1 part by mass of an antifoaming agent, and 10 parts by mass of water.
As a result of the test, no rust, blistering, cracking and peeling were observed in the three coatings after 120 cycles. In addition, no problem was found in storage stability.

（実施例１０）
実施例１０の防錆塗料の組成は合成樹脂エマルジョンとしてのアクリル樹脂エマルジョン（不揮発分５０質量％、ガラス転移点８℃）１２０質量部、水酸化カルシウム２０質量部、水酸化マグネシウム２０質量部、増粘剤１質量部、消泡剤１質量部である。
試験の結果、１２０サイクル後の試験体は３枚中１枚で塗膜に錆、膨れ、割れ及び剥がれは認められなかった。残り２枚は切り込み傷周辺にやや錆の発生が見られた。また、貯蔵安定性に問題は見られなかった。 (Example 10)
The composition of the anticorrosive paint of Example 10 was 120 parts by mass of an acrylic resin emulsion (nonvolatile content 50% by mass, glass transition point 8 ° C.) as a synthetic resin emulsion, 20 parts by mass of calcium hydroxide, 20 parts by mass of magnesium hydroxide, and increased. 1 part by mass of a sticking agent and 1 part by mass of an antifoaming agent.
As a result of the test, one of the three specimens after 120 cycles showed no rust, blistering, cracking or peeling on the coating film. The remaining two sheets were slightly rusted around the cuts. In addition, no problem was found in storage stability.

（実施例１１）
実施例１１の防錆塗料の組成は合成樹脂エマルジョンとしてのアクリル樹脂エマルジョン（不揮発分５０質量％、ガラス転移点８℃）１２０質量部、水酸化カルシウム３５質量部、水酸化マグネシウム１５質量部、増粘剤１質量部、消泡剤１質量部である。
試験の結果、１２０サイクル後の試験体は３枚ともに塗膜に錆、膨れ、割れ及び剥がれは認められなかった。また、貯蔵安定性に問題は見られなかった。 (Example 11)
The composition of the anticorrosive paint of Example 11 was 120 parts by mass of an acrylic resin emulsion (nonvolatile content 50% by mass, glass transition point 8 ° C.) as a synthetic resin emulsion, 35 parts by mass of calcium hydroxide, 15 parts by mass of magnesium hydroxide, and increased. 1 part by mass of a sticking agent and 1 part by mass of an antifoaming agent.
As a result of the test, no rust, blistering, cracking and peeling were observed in the three coatings after 120 cycles. In addition, no problem was found in storage stability.

（参考例１２）
参考例１２の防錆塗料の組成は合成樹脂エマルジョンとしてのアクリル樹脂エマルジョン（不揮発分５０質量％、ガラス転移点８℃）１２０質量部、水酸化カルシウム３５質量部増粘剤１質量部、消泡剤１質量部である。
試験の結果、１２０サイクル後の試験体は３枚中２枚で塗膜に錆、膨れ、割れ及び剥がれは認められなかった。また、貯蔵安定性に問題は見られなかった。
( Reference Example 12)
The composition of the anticorrosive paint of Reference Example 12 is 120 parts by mass of an acrylic resin emulsion (nonvolatile content 50% by mass, glass transition point 8 ° C.) as a synthetic resin emulsion, 35 parts by mass of calcium hydroxide, 1 part by mass of a thickener, defoaming 1 part by mass of the agent.
As a result of the test, rust, blistering, cracking and peeling were not observed in the coating film after 2 out of 3 specimens after 120 cycles. In addition, no problem was found in storage stability.

（参考例１３）
参考例１３の防錆塗料の組成は合成樹脂エマルジョンとしてのアクリル樹脂エマルジョン（不揮発分５０質量％、ガラス転移点８℃）１２０質量部、水酸化カルシウム４５質量部、増粘剤１質量部、消泡剤１質量部である。
試験の結果、１２０サイクル後の試験体は３枚ともに塗膜に錆、膨れ、割れ及び剥がれは認められなかった。また、貯蔵安定性に問題は見られなかった。 ( Reference Example 13)
The composition of the anticorrosive paint of Reference Example 13 is 120 parts by mass of an acrylic resin emulsion (nonvolatile content 50% by mass, glass transition point 8 ° C.) as a synthetic resin emulsion, 45 parts by mass of calcium hydroxide, 1 part by mass of a thickener, 1 part by mass of foaming agent.
As a result of the test, no rust, blistering, cracking and peeling were observed in the three coatings after 120 cycles. In addition, no problem was found in storage stability.

（実施例１４）
実施例１４の防錆塗料の組成は合成樹脂エマルジョンとしてのアクリル樹脂エマルジョン（不揮発分５０質量％、ガラス転移点８℃）１２０質量部、水酸化カルシウム５０質量部、水酸化マグネシウム３０質量部、増粘剤１質量部、消泡剤１質量部である。
試験の結果、１２０サイクル後の試験体は３枚ともに塗膜に錆、膨れ、割れ及び剥がれは認められなかった。また、貯蔵安定性に問題は見られなかった。 (Example 14)
The composition of the anticorrosive paint of Example 14 was 120 parts by mass of an acrylic resin emulsion (nonvolatile content 50% by mass, glass transition point 8 ° C.) as a synthetic resin emulsion, 50 parts by mass of calcium hydroxide, 30 parts by mass of magnesium hydroxide, and increased. 1 part by mass of a sticking agent and 1 part by mass of an antifoaming agent.
As a result of the test, no rust, blistering, cracking and peeling were observed in the three coatings after 120 cycles. In addition, no problem was found in storage stability.

（比較例１）
比較例１の防錆塗料の組成は合成樹脂エマルジョンとしてのアクリル樹脂エマルジョン（不揮発分５０質量％、ガラス転移点−１０℃）１２０質量部、水酸化カルシウム７０質量部、水酸化マグネシウム３０質量部、酸化マグネシウム２質量部、増粘剤１質量部、消泡剤１質量部である。
試験の結果、１２０サイクル後の試験体は３枚ともに塗膜に錆、膨れ、割れ及び剥がれは認められなかった。また、５０℃貯蔵後で粘度上昇が見られた。 (Comparative Example 1)
The composition of the anticorrosive paint of Comparative Example 1 is 120 parts by mass of an acrylic resin emulsion (nonvolatile content 50% by mass, glass transition point-10 ° C) as a synthetic resin emulsion, 70 parts by mass of calcium hydroxide, 30 parts by mass of magnesium hydroxide, 2 parts by mass of magnesium oxide, 1 part by mass of a thickener, and 1 part by mass of an antifoaming agent.
As a result of the test, no rust, blistering, cracking and peeling were observed in the three coatings after 120 cycles. Moreover, the viscosity increase was seen after 50 degreeC storage.

（比較例２）
比較例２の防錆塗料の組成は合成樹脂エマルジョンとしてのアクリルシリコーン共重合樹脂エマルジョン（不揮発分５６質量％、ガラス転移点−１５℃）１２０質量部、水酸化カルシウム１００質量部、水酸化マグネシウム５０質量部、増粘剤１質量部、消泡剤１質量部、水１０質量部である。
試験の結果、１２０サイクル後の試験体は３枚ともに塗膜に錆、膨れ、割れ及び剥がれは認められなかったが、５０℃貯蔵後は粘度上昇し、固まって使用できない状態だった。 (Comparative Example 2)
The composition of the anticorrosive paint of Comparative Example 2 is 120 parts by mass of an acrylic silicone copolymer resin emulsion (nonvolatile content 56% by mass, glass transition point -15 ° C.) as a synthetic resin emulsion, 100 parts by mass of calcium hydroxide, and 50% of magnesium hydroxide. They are 1 part by mass, 1 part by mass of a thickener, 1 part by mass of an antifoaming agent, and 10 parts by mass of water.
As a result of the test, rust, swelling, cracking, and peeling were not observed in the three coatings after 120 cycles, but the viscosity increased after storage at 50 ° C., and it was in a state where it could not be used.

（比較例３）
比較例３の防錆塗料の組成は合成樹脂エマルジョンとしてのアクリル樹脂エマルジョン（不揮発分５０質量％、ガラス転移点８℃）１２０質量部、水酸化カルシウム５０質量部、水酸化マグネシウム４５質量部、増粘剤１質量部、消泡剤１質量部である。
試験の結果、１２０サイクル後の試験体は３枚ともに塗膜に錆、膨れ、割れ及び剥がれは認められなかった。また、５０℃貯蔵にやや粘度上昇が見られた。 (Comparative Example 3)
The composition of the anticorrosive paint of Comparative Example 3 was 120 parts by mass of an acrylic resin emulsion (nonvolatile content 50% by mass, glass transition point 8 ° C.) as a synthetic resin emulsion, 50 parts by mass of calcium hydroxide, 45 parts by mass of magnesium hydroxide, and increased. 1 part by mass of a sticking agent and 1 part by mass of an antifoaming agent.
As a result of the test, no rust, blistering, cracking and peeling were observed in the three coatings after 120 cycles. In addition, a slight increase in viscosity was observed upon storage at 50 ° C.

（比較例４）
比較例４の防錆塗料の組成は合成樹脂エマルジョンとしてのアクリルシリコーン共重合樹脂エマルジョン（不揮発分５６質量％、ガラス転移点−１５℃）１２０質量部、増粘剤１質量部、消泡剤１質量部、水１０質量部である。
試験の結果、１２０サイクル後の試験体は３枚ともに塗膜に錆、膨れ、割れ及び剥がれが認められた。また、貯蔵安定性に問題は見られなかった。 (Comparative Example 4)
The composition of the anticorrosive paint of Comparative Example 4 is 120 parts by mass of an acrylic silicone copolymer resin emulsion (non-volatile content 56% by mass, glass transition point -15 ° C.) as a synthetic resin emulsion, 1 part by mass of a thickener, and an antifoaming agent 1 It is 10 parts by mass of water and 10 parts by mass of water.
As a result of the test, rust, blistering, cracking and peeling were observed in the coating film of all three specimens after 120 cycles. In addition, no problem was found in storage stability.

Claims (4)

（ａ）水酸化カルシウムと水酸化マグネシウムと、（ｂ）合成樹脂エマルジョンとを含有する防錆塗料であって、
前記防錆塗料に含有される水分の質量を１００質量部とした場合、前記（ａ）成分の質量が６０〜１４０質量部であり、
前記（ｂ）成分の不揮発分１００質量部に対する前記（ａ）成分の質量が５０〜１５０質量部であることを特徴とする防錆塗料。 (A) calcium hydroxide and magnesium hydroxide, a rust preventive paint containing the (b) a synthetic resin emulsion,
When the mass of moisture contained in the rust preventive paint is 100 parts by mass, the mass of the component (a) is 60 to 140 parts by mass,
The rust preventive paint, wherein the mass of the component (a) is 50 to 150 parts by mass with respect to 100 parts by mass of the nonvolatile content of the component (b). 前記水酸化カルシウムの含有量を１００質量部としたときの水酸化マグネシウムの含有量が３０〜７５質量部であることを特徴とする請求項１に記載の防錆塗料。 The rust preventive paint according to claim 1, wherein the content of magnesium hydroxide is 30 to 75 parts by mass when the content of calcium hydroxide is 100 parts by mass . リン成分、遷移金属、第１２族元素、第１３族元素及びこれらの塩を実質的に含有しないことを特徴とする請求項１又は２に記載の防錆塗料。 The rust preventive paint according to claim 1 or 2, which is substantially free of a phosphorus component, a transition metal, a Group 12 element, a Group 13 element and salts thereof . 前記（ｂ）合成樹脂エマルジョンのガラス転移点が２５〜−４０℃であることを特徴とする請求項１〜３のいずれかに記載の防錆塗料。
The rust preventive paint according to any one of claims 1 to 3, wherein the glass transition point of the (b) synthetic resin emulsion is 25 to -40 ° C.
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