JPS6257472A - Water-soluble rust-preventive paint - Google Patents

Abstract

PURPOSE:To provide a water-soluble rust-preventive paint composed of PVA and a small amount of alpha-nitroso-beta-naphthol, having excellent oil-resistance, heat-resistance and hot-oil resistance and applicable to an oil-immersed electrical apparatus, etc. CONSTITUTION:The objective paint can be produced by compounding (A) 100 pts.(wt.) of PVA with (B) 1-10pts. of alpha-nitroso-beta-naphthol and (C) preferably 300-800pts. of ion-exchanged water. The paint may be further compounded with (D) preferably 25-35pts. of carbon black or titanium dioxide fine powder, (E) preferably 1-3pts. of ultrafine silica anhydride particles (e.g. having particle diameter of about 0.012mu) and (F) preferably 10-20pts. of a hardly water-soluble metal oxide (e.g. silica gel) or inorganic salt (e.g. calcium carbonate).

Description

【発明の詳細な説明】 ［産業上の利用分野］ 本発明は、水溶性防錆塗料に閃する。さらに詳しくは、
耐油性、耐熱性、耐熱油性に優れた水溶性防錆塗料に関
する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention is directed to water-soluble anticorrosive paints. For more details,
It relates to a water-soluble anti-corrosion paint with excellent oil resistance, heat resistance, and heat oil resistance.

［従来の技術］ 従来の水溶性防錆塗料には、一般に固体被膜を形成しな
い１次防錆剤と固体被膜を形成する２次防錆剤の２種類
が用いられている。[Prior Art] Two types of conventional water-soluble rust preventive paints are generally used: a primary rust preventive agent that does not form a solid film, and a secondary rust preventive agent that forms a solid film.

１次防錆剤には低分子量の有機化合物が多く用いられて
いるが、常温で容易に絶縁油などに溶解し、耐油性がわ
るい。また２次防錆剤にはポリアクリル系の高分子化合
物が多く用いられているが、１００℃前後で分解し、絶
縁油などに溶解することがあり、耐熱性がわるい。Low molecular weight organic compounds are often used as primary rust preventive agents, but they easily dissolve in insulating oil at room temperature and have poor oil resistance. Further, polyacrylic polymer compounds are often used as secondary rust preventive agents, but they decompose at around 100° C. and may dissolve in insulating oil, etc., resulting in poor heat resistance.

［発明が解決しようとする問題点１ 前記のように従来の水溶性防錆塗料は絶縁油中での耐油
性、耐熱性あるいは耐熱油性がわるく、高度の絶縁性能
が要求される油入電気機器などで使用することは好まし
くない。[Problem to be solved by the invention 1 As mentioned above, conventional water-soluble anti-rust paints have poor oil resistance, heat resistance, or hot oil resistance in insulating oil, and are used in oil-filled electrical equipment that requires high insulation performance. It is not recommended to use it as such.

本発明は、前記のような問題点を解決するためになされ
たものであり、耐油性、耐熱性および耐熱油性に優れた
水溶性防錆塗料を提供することを目的とする。The present invention was made in order to solve the above-mentioned problems, and an object of the present invention is to provide a water-soluble anticorrosive paint having excellent oil resistance, heat resistance, and hot oil resistance.

［問題を解決するための手段１ 本発明においてポリビニルアルコール（以下、ＰＶＡと
いう）１００重量部および構造式（■）：Ｏ で示されるα−ニトロソ−β−ナフトール１〜１０重量
部から製造される水溶性防錆塗料に関する。[Means for solving the problem 1 In the present invention, polyvinyl alcohol (hereinafter referred to as PVA) is manufactured from 100 parts by weight of polyvinyl alcohol (hereinafter referred to as PVA) and 1 to 10 parts by weight of α-nitroso-β-naphthol represented by the structural formula (■): O Regarding water-soluble anti-rust paint.

さらに詳しくは、一般に水溶性の接着剤として、また１
２０℃前後の温度でも耐油性に優れていることから油入
電気機器内の絶縁物の接着剤として使用されている２１
３１００重量部および絶縁油などの特性を低下させるこ
とがなく、銅、コバルト、鉄などと定量的に反応する非
イオン性の化合物であるａ−ニトロン−β−ナフトール
１〜１０重量部からなる２次防錆塗料である水溶性防錆
塗料に関する。More specifically, it is generally used as a water-soluble adhesive;
Because it has excellent oil resistance even at temperatures around 20°C, it is used as an adhesive for insulation in oil-filled electrical equipment21
3,100 parts by weight and 1 to 10 parts by weight of a-nitrone-β-naphthol, which is a nonionic compound that quantitatively reacts with copper, cobalt, iron, etc. without deteriorating the properties of insulating oil, etc. This article relates to a water-soluble anti-corrosion paint that is an anti-rust paint.

［実施例］ 本発明においてはＰＶＡ１００重量部およびα−ニトロ
ソ−β−ナフトール〜１０重量部から水溶性防錆塗料か
えられる。[Example] In the present invention, 100 parts by weight of PVA and ~10 parts by weight of α-nitroso-β-naphthol are used as the water-soluble anticorrosive paint.

前記Ｐｖ＾およびα−ニトロン−β−す７トールは一般
に市販されているものを使ってもさしつかえなく、２１
３１００重量部に対してα−ニトロン−β−ナフトール
１〜１０！１！量部を調合し、これをイオン交換水に溶
解させて作製する。また、前記Ｐｖ＾およびａ−ニトロ
ン−β−す７）−ルは別々にイオン交換水に溶解させて
から調合してもよい。As the Pv^ and α-nitrone-β-7tol, commercially available products may be used, and 21
α-nitrone-β-naphthol 1 to 10!1 per 3100 parts by weight! It is prepared by preparing a certain amount and dissolving it in ion-exchanged water. Alternatively, the Pv^ and a-nitrone-β-su7)-l may be separately dissolved in ion-exchanged water and then blended.

前記Ｐｖ＾は防錆作用を永続させる成分であり、これに
防錆効果のあるα−ニトロン−β−す７トールを添加さ
せると優れた防錆効果が期待できるが、ＰＶＡ１００重
量部に対してα−ニトロン−β−ナフトール１重量未満
だと、防錆効果が小さく、また１０重量部をこえると塗
膜強度が弱くなるので、１〜１０重量部添加するのが好
ましい。The above Pv^ is a component that makes the rust preventive effect permanent, and if α-nitrone-β-su7tol, which has a rust preventive effect, is added to it, an excellent rust preventive effect can be expected. If it is less than 1 part by weight of α-nitrone-β-naphthol, the antirust effect will be small, and if it exceeds 10 parts by weight, the strength of the coating will be weakened, so it is preferable to add 1 to 10 parts by weight.

また、前記Ｐｖ＾を溶解させるためのイオン交換水け２
１３１００重量部に対して３００重量部未満であればＰ
ＶＡは溶けにくく、また８００重量部をこえると塗膜強
度が弱くなるので３００〜８００重量部で用いるのが好
ましい。In addition, ion exchange water 2 for dissolving the Pv^
P if it is less than 300 parts by weight for 13100 parts by weight
VA is difficult to dissolve, and if it exceeds 800 parts by weight, the strength of the coating becomes weak, so it is preferably used in an amount of 300 to 800 parts by weight.

こうしてえちれた防錆塗料は、塗膜の厚さが約３０μ肩
になるように塗布し、気温Ｏ〜４０℃の大気中で自然乾
燥させて用いられる。The anticorrosive paint thus etched is applied to a coating film thickness of approximately 30 μm, and is used by drying naturally in the atmosphere at a temperature of 0 to 40°C.

また前記水溶性防錆塗料中の２１３１００重量部に対し
てカーボンブラック２５〜３５重量部、超微粒子状の無
水シリカ１〜３重量部、金属酸化物あるいは無機塩類の
微粒子１０〜２０重量部を添加させてもよ（１゜ 前記カーボンブラックは一般に黒色顔料として使用され
ているが、前記水溶性防錆塗料中のＰＶＡ１００重量部
に対して３５重量部をこえて添加すると、塗膜の密着性
がわるくなり、また２５重量部未満では着色効果がわる
くなるので２５〜３５重量部添加するのが好ましい。Furthermore, 25 to 35 parts by weight of carbon black, 1 to 3 parts by weight of ultrafine anhydrous silica, and 10 to 20 parts by weight of fine particles of metal oxides or inorganic salts are added to 213,100 parts by weight of the water-soluble antirust paint. (1゜The carbon black is generally used as a black pigment, but if it is added in an amount exceeding 35 parts by weight to 100 parts by weight of PVA in the water-soluble anti-corrosion paint, the adhesion of the paint film will deteriorate. If the amount is less than 25 parts by weight, the coloring effect will be poor, so it is preferable to add 25 to 35 parts by weight.

前記超微粒子状無水シリカとは粒径が約０．０１２μ肩
程度の無水シリカといい、Ｐｖ八へ膜と下地金属との密
着性を向上させるための成分であるが、前記水溶性防錆
塗料中の２１３１００重量部に対して３重量部をこえる
と、粘度が増大しすぎ、また１重量部未満では塗膜のＶ
着性がわるくなるので１〜３重量部添加するのが好まし
い。The ultrafine particulate anhydrous silica is anhydrous silica with a particle size of approximately 0.012 μm, and is a component for improving the adhesion between the Pv8 film and the underlying metal. If it exceeds 3 parts by weight compared to 213,100 parts by weight, the viscosity will increase too much, and if it is less than 1 part by weight, the V of the coating film will increase.
It is preferable to add 1 to 3 parts by weight since the adhesion properties will deteriorate.

前記水難溶性の金属酸化物あるいは無機塩類は塗膜の硬
度を大さくするための成分であるが、前記水溶性防錆塗
料中のＰＶＡ１００重量部に対して２０重量部をこえる
と塗膜のｆｆｉ着性がわるくなり、また１０重量部未満
では塗膜の硬度を大きくする効果が小さいので１０〜２
０重量部添加するのが好ましい。The slightly water-soluble metal oxides or inorganic salts are components for increasing the hardness of the paint film, but if it exceeds 20 parts by weight per 100 parts by weight of PVA in the water-soluble anticorrosion paint, the ffi of the paint film will increase. If the adhesion is less than 10 parts by weight, the effect of increasing the hardness of the coating film will be small.
It is preferable to add 0 parts by weight.

金属酸化物の具体例としてシリカゾル、アルミナなど、
また前記無機塩類の具体例として炭酸カルシウム、硫酸
バリウムなどをあげることができる。Specific examples of metal oxides include silica sol, alumina, etc.
Specific examples of the inorganic salts include calcium carbonate and barium sulfate.

また前記カーボンブラックのかわりに白色顔料として使
用されている二酸化チタン微粒子を直接前記水溶性防錆
塗料に添加させてもよい、このばあい二酸化チタンの微
粒子とは粒径が約１０μｌの粒子をいい、３５重量部を
こえると密着性がわるくなり、また２５重量部未満では
着色効果が小さいので２５〜３０重量部を添加するのが
好ましい。Further, titanium dioxide fine particles, which are used as a white pigment, may be added directly to the water-soluble antirust paint instead of the carbon black. In this case, the titanium dioxide fine particles are particles with a particle size of about 10 μl. If it exceeds 35 parts by weight, the adhesion will deteriorate, and if it is less than 25 parts by weight, the coloring effect will be small, so it is preferable to add 25 to 30 parts by weight.

さらに乾燥をはやめるためにエタノールあるいはエタノ
ールベースの変性アルコールを添加する水量の１０重量
％以上添加してもよい。Furthermore, in order to prevent drying, ethanol or ethanol-based denatured alcohol may be added in an amount of 10% by weight or more based on the amount of water to be added.

つぎに本発明の水溶性防錆塗料を実施例に基づいてさら
に詳細に説明するが、本発明はかかる実施例のみに限定
されるものではない。Next, the water-soluble anticorrosive paint of the present invention will be explained in more detail based on Examples, but the present invention is not limited to these Examples.

実施例１〜３ 完全ケン化型Ｐｖ＾１００重量部に市販の試薬特級のａ
−ニトロソ−β−す７トールを第１表に示したように添
加し、各々水温８０℃のイオン交換水５００重量部中に
充分に攪拌して溶解させて水溶性防ｔｊ４塗料をえた。Examples 1 to 3 Completely saponified Pv^100 parts by weight of commercially available reagent special grade a
-Nitroso-β-7toll was added as shown in Table 1, and dissolved in 500 parts by weight of ion-exchanged water at a water temperature of 80°C with sufficient stirring to obtain a water-soluble anti-TJ4 paint.

えちれた水溶性防錆塗料の防錆力、粘度、粘着度、塗料
膜の硬度および油汚染性試験後の絶縁油の体積抵抗率、
誘電正接、界面張力、全酸価を測定した結果を第２表に
示す。Rust preventive power, viscosity, tackiness, hardness of paint film, and volume resistivity of insulating oil after oil staining test of water-soluble rust preventive paint,
Table 2 shows the results of measuring the dielectric loss tangent, interfacial tension, and total acid value.

なお各特性は、それぞれつぎの方法にしたがって測定し
た。Note that each characteristic was measured according to the following method.

（ａ）防錆力 前記えられた水溶性防錆塗料を１５ＱｚｚＸ　１００＋
＋ｖの５Ｓ４１鋼板上に塗料の厚さが約３０μｌとなる
ように室温中で塗布したのち、室温で約４時間自然乾燥
させた。そののち気温４０℃、相対湿度９５％の雰囲気
中に暴露させ、発錆するまでの時間を測定した。(a) Rust-preventing power The obtained water-soluble rust-preventing paint is 15QzzX 100+
The paint was applied to a thickness of about 30 μl on a +V 5S41 steel plate at room temperature, and then air-dried at room temperature for about 4 hours. Thereafter, it was exposed to an atmosphere of a temperature of 40° C. and a relative humidity of 95%, and the time required for rust to develop was measured.

（ｂ）粘度 室温で東京計器製Ｂ型粘度計を用いて測定した。(b) Viscosity Measurement was performed at room temperature using a B-type viscometer manufactured by Tokyo Keiki.

（ｃ）粘着度（基盤目） 塗膜上にｌｚｘ角の基盤目１００個をナイフで作り、テ
ープを貼付したのち、テープをはがしたときに基盤目の
塗膜が剥離しなかった個数を測定した。(c) Adhesiveness (base marks) After making 100 base marks of lzx angle on the paint film with a knife and pasting the tape, calculate the number of base marks that did not peel off when the tape was removed. It was measured.

（ｄ）塗料膜の硬度 前記＜ａ＞で行なったＩｋ１１Ｆ７日後の塗膜の硬度と
暴露を行なう前の塗膜の硬度の変化について鉛筆を用い
て調べた。(d) Hardness of paint film The hardness of the paint film 7 days after the Ik11F exposure conducted in <a> above and the change in hardness of the paint film before exposure were examined using a pencil.

（ｅ）油汚染性試験後の絶縁油の体積抵抗率、誘電正接
、界面張力、全酸価 油汚染性試験として前記でえちれた水溶性防錆塗料を４
ＱＩＩＸ３０１ｍの５Ｓ４１１３１Ｉ板上に塗料の厚さ
が約３０μ瀧となるように室温中で塗布したのち室温で
約４時間乾燥させた。そののち１２０℃の絶縁油中で約
２００時間加熱した。(e) Volume resistivity, dielectric loss tangent, interfacial tension, and total acid value of insulating oil after oil staining test.
The coating material was coated on a QIIX 301m 5S41131I board at room temperature to a thickness of about 30 μm, and then dried at room temperature for about 4 hours. Thereafter, it was heated in insulating oil at 120°C for about 200 hours.

っぎにＪＩＳ　Ｃ−２１０１の方法にしたがって、前記
絶縁油の温度８０℃での体積抵抗率と誘電正接、界面張
力および全酸価を測定した。According to the method of JIS C-2101, the volume resistivity, dielectric loss tangent, interfacial tension, and total acid value of the insulating oil at a temperature of 80° C. were measured.

実施例４〜８ 実施例２でえられた水溶性防錆塗料に粒径的０．０１２
μ屑の透徹粒子状の無水ンリカ（日本アエロジル（株）
！！、７　工ａ　シル２００）ヲＰＶＡ１００！ｉ　ｆ
ｋｕ　ｌ：　Ｎして第１表に示したように添加し、よく
攪拌してあらたに水溶性防錆塗料をえた。Examples 4 to 8 The water-soluble antirust paint obtained in Example 2 had a particle size of 0.012.
Transparent particulate anhydrous acid of μ-dust (Nippon Aerosil Co., Ltd.)
! ! , 7 engineering a sill 200) wo PVA 100! If
ku l: N was added as shown in Table 1, and the mixture was thoroughly stirred to obtain a new water-soluble antirust paint.

えられた水溶性防錆塗料の各特性は実施例１〜３に記載
した方法にしたがって測定した。その測定結果を第２表
に示す。Each characteristic of the obtained water-soluble anticorrosive paint was measured according to the methods described in Examples 1-3. The measurement results are shown in Table 2.

実施例９〜１２ 実施例４でえちれた水溶性防錆塗料に粒径約１０μ肩の
無水ケイ酸および顔料としてカーボンブラックまたは酸
化チタンを第１表に示したように添加し、よ（攪拌して
水溶性防錆塗料をえた。Examples 9 to 12 Silicic anhydride with a particle size of about 10 μm and carbon black or titanium oxide as a pigment were added to the water-soluble anticorrosive paint prepared in Example 4 as shown in Table 1. A water-soluble anti-corrosion paint was obtained by stirring.

えられた水溶性防錆塗料の各特性は実施例１〜３に記載
した方法にしたがって測定した。その結果を第２表に示
す。Each characteristic of the obtained water-soluble anticorrosive paint was measured according to the methods described in Examples 1-3. The results are shown in Table 2.

実施例１３お上り１４ 実施例１１でえられた水溶性防錆塗料に第１表に示され
る組成になるように変性アルコールとしてエキネンＦ−
１（日本アルコール販売（株）！りをＰＶＡの水溶液に
添加してあらたにえられた水溶性防錆塗料の各特性のを
実施例１〜３に記載した方法にし比較例１〜５ 従来の水溶性防錆塗料として第３表に示した市販の防錆
塗料を用いて各特性を実施例１〜３に記載した方法にし
たがって測定した。測定した結果は第５表に示す・ 比較例６〜８ 比較例６としてＰｖ＾１００重量部にイオン交換水５０
０重量部添加してえられた水溶性防錆塗料のほか、第４
表に示したように鉄と反応するタンニンおよび市販の防
錆塗料を添加して比較例７および比較例８の水溶性防錆
塗料を作製し、各特性を実施例１〜３に記載した方法に
したがって測定した。Example 13 Ascendant 14 Echinen F- was added to the water-soluble anti-corrosion paint obtained in Example 11 as denatured alcohol so that it had the composition shown in Table 1.
1 (Nippon Alcohol Sales Co., Ltd.) was added to an aqueous solution of PVA to obtain a new water-soluble antirust paint. Using the commercially available antirust paints shown in Table 3 as water-soluble antirust paints, each characteristic was measured according to the methods described in Examples 1 to 3.The measured results are shown in Table 5. Comparative Example 6 ~8 As Comparative Example 6, 50 parts by weight of ion-exchanged water was added to 100 parts by weight of Pv^.
In addition to the water-soluble antirust paint obtained by adding 0 parts by weight,
The water-soluble antirust paints of Comparative Examples 7 and 8 were prepared by adding tannins that react with iron and commercially available antirust paints as shown in the table, and the respective properties were described in Examples 1 to 3. Measured according to.

測定した結果は第５表に示す。The measured results are shown in Table 5.

なお、実施例１〜１４および参考例１〜８について防錆
力および油汚染性試験後の絶縁油の特性評＃４３表 注）比較例１ニ一次防錆剤、比較例２〜５二二次防錆剤
第４表 ［発明の効果１ 以上述べたように、本発明の水溶性防錆塗料は安価なＰ
ＶＡおよびａ−ニトロソ−β−す７トールからなり、耐
油性、耐熱性、耐熱油性に優れているので、高度の絶縁
性能が要求される種々の油入電気機器などで使用するば
あいには、絶縁油の各ａ特性を低下させずに用いること
ができるという効果を奏する。In addition, for Examples 1 to 14 and Reference Examples 1 to 8, properties evaluation of insulating oil after rust preventive power and oil staining test #43 Table Note) Comparative Example 1 Primary rust inhibitor, Comparative Examples 2 to 5 2 Rust preventive agent Table 4 [Effect of the invention 1 As stated above, the water-soluble rust preventive paint of the present invention is an inexpensive P
It is composed of VA and a-nitroso-β-7-thol and has excellent oil resistance, heat resistance, and hot oil resistance, so it is suitable for use in various oil-filled electrical equipment that requires a high degree of insulation performance. , it is possible to use the insulating oil without degrading each of the a characteristics.

Claims (3)

【特許請求の範囲】[Claims] （１）ポリビニルアルコール１００重量部およびα−ニ
トロソ−β−ナフトール１〜１０重量部からなることを
特徴とする水溶性防錆塗料。(1) A water-soluble anticorrosive paint characterized by comprising 100 parts by weight of polyvinyl alcohol and 1 to 10 parts by weight of α-nitroso-β-naphthol. （２）前記ポリビニルアルコール１００重量部に対しで
カーボンブラック２５〜３５重量部、超微粒子状の無水
シリカ１〜３重量部、水難溶性の金属酸化物あるいは無
機塩類の微粒子１０〜２０重量部を添加したことを特徴
とする特許請求の範囲第（１）項記載の水溶性防錆塗料
。(2) To 100 parts by weight of the polyvinyl alcohol, add 25 to 35 parts by weight of carbon black, 1 to 3 parts by weight of ultrafine anhydrous silica, and 10 to 20 parts by weight of slightly water-soluble metal oxide or inorganic salt particles. A water-soluble anticorrosive paint according to claim (1), characterized in that: （３）前記ポリビニルアルコール１００重量部に対して
二酸化チタンの微粒子２５〜３５重量部、超微粒子状の
無水シリカ１〜３重量部、水難溶性の金属酸化物あるい
は無機塩類の微粒子１０〜２０重量部を添加したことを
特徴とする特許請求の範囲第（１）項記載の水溶性防錆
塗料。(3) 25 to 35 parts by weight of fine particles of titanium dioxide, 1 to 3 parts by weight of ultrafine anhydrous silica, and 10 to 20 parts by weight of fine particles of poorly water-soluble metal oxides or inorganic salts based on 100 parts by weight of the polyvinyl alcohol. The water-soluble rust-preventing paint according to claim (1), characterized in that it contains: