WO2003060197A1 - Inhibiteur de corrosion solide et volatil - Google Patents

Inhibiteur de corrosion solide et volatil Download PDF

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Publication number
WO2003060197A1
WO2003060197A1 PCT/JP2003/000297 JP0300297W WO03060197A1 WO 2003060197 A1 WO2003060197 A1 WO 2003060197A1 JP 0300297 W JP0300297 W JP 0300297W WO 03060197 A1 WO03060197 A1 WO 03060197A1
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WO
WIPO (PCT)
Prior art keywords
water
acid
nitrite
protective agent
powder
Prior art date
Application number
PCT/JP2003/000297
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English (en)
Japanese (ja)
Inventor
Nobuyoshi Nambu
Kazuhiko Arimatsu
Toshimitsu Hamaguchi
Original Assignee
Chubu Chelest Co., Ltd.
Chelest Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Chubu Chelest Co., Ltd., Chelest Corporation filed Critical Chubu Chelest Co., Ltd.
Publication of WO2003060197A1 publication Critical patent/WO2003060197A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/02—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in air or gases by adding vapour phase inhibitors

Definitions

  • the present invention relates to a vaporizable solid protective agent, for example, when storing, transporting, or transporting devices and parts made of a metal that is easily oxidized, such as various mechanical parts made of steel and automobile parts.
  • a vaporizable solid protective agent to prevent its surface from being oxidized and emitted, and exhibits an excellent protective effect especially in both short term and long term.
  • This is a vaporizable solid inhibitor that does not cause contamination due to adhesion to the component surface.
  • VCI Volatile Corrosion Inhibitor
  • a typical example is a sublimable cyclohexylamine carbonate [(Ce ! H i NH) 2 HCO 2 : CHC]
  • Ya diisopropyl Seo Pro Piruami emissions nitrite salt ⁇ [(CH 3) 2 CH ] 2 NH - HN 0 2: DIPAN ⁇ Jishiku to b Kishiruami emissions nitrite [(C e H i J 2 ⁇ ⁇ ⁇ NO 2 : DICHAN] is known.
  • CHC exhibits excellent initial protection, but has a strong odor, and its vapor pressure is as high as AX l O — imm H g (25 ° C).
  • the packaging must be strictly performed.
  • DICHAN is long although the anti ⁇ is better, the vapor pressure 1 X 1 0 - lower 4 mmH g (2 5), because of Yosu 2 0 hours or more to exert Bo ⁇ effect Lack of initial defense capability. Further, if the distance from the article to be protected is more than 20 to 30 cm, a sufficient protection effect is not exhibited.
  • the vapor pressure of DIPAN is 5 X 1 0 - Ri 3 mm H g (2 5 ° C) intermediate der of CHC and DICHAN, although has both excellent initial anti ⁇ and long proof ⁇ , which It is known that when left in the air, a part of it is altered to form diisopropyl-N-nitrosoamine, and the diisopropyl-N-nitrosoamine is produced. Has been suggested to be carcinogenic (H. DRUCKRW, R. PREUSSMANN, etc; Zeitshrift fur Kreb forscreen 69, 103-201, 1967), and its use has been evaded from the health point of view. Tend to be.
  • Japanese Patent Application Laid-Open Nos. H10-114,92-92 and H11-1131,872 developed by the present applicants.
  • the technology disclosed in Japanese Patent Application Laid-Open No. H10-114894 is a mixture of nitrite, a pH buffer, and benzotriazole.
  • Japanese Unexamined Patent Publication No. Hei 11-3153887 discloses a mixture of DICHAN, an organic or inorganic ammonium salt, and a water retention agent such as a crystalline cell orifice. In defense of Chip.
  • any of initial protective properties, long-term protective properties and long-range effective reach performance It has excellent performance, does not cause any health problems, and has excellent protection against hot and humid conditions where mackerel is likely to occur.
  • the aim of providing a vaporizable solid antioxidant that can be suppressed as far as possible research was repeated, and as a part of this, the vaporizable solid anti-spearing agent disclosed in Japanese Patent Application Laid-Open No. 13_316966 was developed. Proposed earlier.
  • the vaporizable solid inhibitor comprises an organic amine and / or metal nitrite, an inorganic acid and an ammonium salt of Z or an organic acid, a metal bicarbonate, and a water-retaining or water-release auxiliary. Incorporated as an essential ingredient, it has excellent protection against both short and long term, exhibits excellent protection even in a high humidity atmosphere, and has a tablet or powder form. It is evaluated as very excellent because it has excellent handleability and does not adhere to and contaminate the protected object.
  • this volatile solid inhibitor has room for improvement in the following points.
  • the vaporizable solid protective agent since the vaporizable solid protective agent has a very high hydrolysis reactivity of the protective active ingredient, it is necessary to minimize the water content in the raw material during the production, so that strict production control is required.
  • a high-barrier film such as aluminum-deposited film or silica-deposited film
  • the active ingredient was decomposed and vaporized at an early stage, and the active ingredient was lost.
  • the present invention has been made in view of the above situation, Its purpose is to reduce the loss of vaporization of the active ingredient even when it is packaged and stored, for example, in a general-purpose polyethylene film with a film thickness of about 60 m, simplifying production management and storage management. In addition, it shows excellent protection performance in both short term and long term, exhibits excellent protection effect even in high humidity atmosphere, and has excellent storage stability, An object of the present invention is to provide a vaporizable solid protective agent having the characteristics that it is powdery and has excellent handleability and does not adhere to and contaminate an object to be protected. Disclosure of the invention
  • the vaporizable solid protective agent of the present invention that can solve the above-mentioned problems includes an organic and / or inorganic nitrite, a water-retaining and / or water-sustained release auxiliary, and an acid substance. There is a gist when it is included as an essential component.
  • the active ingredient in the present invention, if the above active ingredient is formed into tablets, powders, granules, or the like, and preferably commercialized by being enclosed in a nonwoven fabric or a gas-permeable foam sheet, the active ingredient can be used at the time of use. This is convenient because it does not scatter when stored.
  • nitrites are dicyclohexylamine nitrite, sodium nitrite, lithium nitrite, and calcium nitrite.
  • the water-retaining and / or water-sustained release auxiliary are water-absorbing resins, hygroscopic powders, animal fibers, vegetable fibers, regenerated fibers, synthetic fibers, activated carbon fibers, and the like. If necessary, two or more can be used in combination.
  • the water-retentive and / or water sustained-release aid is described in detail below. As described above, it has an appropriate water retention property and also has an action of releasing an appropriate amount of water in a dry atmosphere. In order to effectively exert such a function, the water retention rate required by the following method must be 0.1 to 0.1. Those in the range of 100% are particularly preferred.
  • water retention and / or water sustained release auxiliary having such a water retention ratio
  • cellulosic fiber powders such as pulp powder.
  • sodium benzoate and anhydrous sulfuric acid Powders such as sodium, polyvinyl alcohol and carboxymethyl cellulose are also preferably used.
  • the acid substance include inorganic acid powders, inorganic acid metal salt powders, and organic acid powders having a function of acidifying PH when the active ingredient exhibiting a protective function is dissolved in water. Or a powder of a salt obtained by partially neutralizing an organic acid with an alkali metal.
  • Preferred specific examples of the inorganic acid include sodium hydrogen sulfate, potassium hydrogen sulfate, and dihydrogen phosphate. Tritium, calcium dihydrogen phosphate, calcium dihydrogen phosphate, pyrrolic acid, boric acid, and the like.
  • Preferred examples of the organic acid include aliphatic carboxylic acid, aromatic power Preferred examples of powders of rubonic acid and their acid anhydrides, oxycarboxylic acid, polyaminocarboxylic acid, and ascorbic acid, and a salt powder obtained by partially neutralizing an organic acid with an alkali metal are succinic acid.
  • a preferable content ratio of the nitrite and the water-retaining and / or water sustained-release auxiliary is 99.9: 0.1 to 10:90, more preferably a mass ratio.
  • the preferred content ratio between the nitrite and the water-retaining and Z or water sustained-release auxiliary and the acid content is the mass ratio of 9: 1 to 20: 80.
  • the range is from 80:20 to 99.9: 0.1, more preferably from 90:10 to 99: 1.
  • the vaporizable solid protective agent of the present invention comprises an organic and / or inorganic nitrite and a water-retaining and / or water-releasing auxiliary (hereinafter sometimes referred to as a water-retaining auxiliary). And an acid substance as essential components.
  • the organic and Z or inorganic nitrites which are active ingredients, do not easily hydrolyze even in the presence of some water, Decomposition vaporization is accelerated only when acidic water is present. Therefore, in the present invention, the decomposition and vaporization of nitrite occurs only when the acid substance is absorbed and dissolved by water, but the acidic water is generated only by absorbing a certain amount of water and dissolving the acid substance in the water. In other words, in the vaporizable solid protective agent of the present invention, the absorption of moisture is rate-determining, and the decomposition and vaporization of nitrite occurs.
  • the active ingredient is formed into tablets, powders, granules, etc., and preferably commercialized by being enclosed in a nonwoven fabric or a breathable sheet, the active ingredient during storage is lost. Also, after opening, it shows excellent protection function in both short term and long term. In addition, there is no danger that the active ingredient in the form of powder or the like is scattered and adheres to the object to be protected and contaminates it.
  • nitrites that can meet such a purpose, and particularly preferred are dicyclohexylamine nitrite, sodium nitrite and potassium nitrite. And calcium nitrite, which can be used alone or in combination of two or more as necessary. Of these, dicyclohexylamine nitrite is particularly preferred.
  • the acid substance may be any substance that dissolves in water absorbed by a water-absorbing auxiliary agent to be described later and generates acidic water, and may be an inorganic acid powder, an inorganic acid metal salt powder, or an organic acid soluble in water. And powders of salts obtained by partially neutralizing organic acids with alkali metals.
  • Preferred specific examples of the inorganic acids and salts thereof include sodium hydrogen sulfate, potassium hydrogen sulfate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, and dihydrogen phosphate.
  • Preferred examples of the organic acid include aliphatic carboxylic acids such as oxalic acid and succinic acid, and aromatic acids such as benzoic acid and fluoric acid.
  • Acid anhydrides such as aromatic carboxylic acids and maleic anhydride; oxycarboxylic acids such as linoleic acid and citric acid; polyaminocarboxylic acids such as ethylenediaminetetraacetic acid; other ascorbic acids; and organic acids such as alkali metals. Salts partially neutralized with Specific examples include sodium sodium succinate and sodium sodium ethylenediaminetetraacetate. These acid substances can be used alone or, if necessary, in combination of two or more kinds.
  • the water retention aid is an essential component in generating acidic water by dissolving the acid substance and promoting the decomposition and vaporization of nitrite.
  • a water absorbing resin a moisture absorbing resin Powders of saccharides having a large number of hydroxyl groups in the compound, such as water-soluble powders, animal fibers, vegetable fibers, regenerated fibers, synthetic fibers, and activated carbon fibers; hygroscopic powders and hygroscopic powders such as lipoxymethyl cellulose; Any material having an appropriate water retention may be used.
  • hygroscopic resin powder animal fibers such as wool, vegetable fibers such as cotton and hemp, and regenerated fibers such as viscose rayon. It is at least one selected from various hydrophilic synthetic fibers and activated carbon fibers. Particularly preferred as fibers are cellulose fiber powders.
  • the water retention aid has an appropriate water retention property and has an action of releasing a suitable amount of water in a dry atmosphere.
  • the water retention obtained by the above method is in the range of 0.1 to 100%, and particularly preferably in the range of 1 to 50%.
  • the water retention aid having such a water retention rate are cellulosic fiber powders, such as pulp powder, and, in addition, sodium benzoate and anhydrous sodium sulfate. Powders such as sodium, polyvinyl alcohol and carboxymethyl cellulose are also preferably used.
  • the preferred content ratio of each of the above components in the vaporizable solid antioxidant of the present invention is such that the ratio of the nitrite to the water retention aid is expressed by mass ratio
  • the sum of nitrite and water-retention aid and the ratio of acid substance are 80:20 to 99.9: 0.1 by mass ratio. Range.
  • the preferred ratio of the nitrite, the water-retaining auxiliary and the acid substance is 95 to 10Z4.9 to 80 / 0.1 to 10%. If the water-retention aid is less than 4.9 and the acid substance is less than 0.1, the initial protective performance tends to be insufficient. If the water-retention aid exceeds 80, the amount of nitrite is relatively small.
  • the long-term protection becomes insufficient, and if the acid substance exceeds 10, the initial protection becomes too strong, so that the initial vaporization of nitrite becomes unnecessarily large, and the long-term protection becomes poor. The tendency to become lower appears.
  • the composition is set within the above-mentioned range, the powdery or granular vaporizable solid protective agent having excellent performance in both initial protective performance and long-term protective performance during use can be obtained. Can be.
  • the essential components constituting the vaporizable solid antioxidant of the present invention are the above-mentioned three types. If necessary, an appropriate amount of a binder, an extender, a pigment, a pigment, or the like may be further blended. It can be used as a mixed powder, or as granules, granules or tablets granulated by any method.
  • the above-mentioned powders, granules, tablets, etc. should be wrapped with a non-woven cloth, or perforated film or open-cell tie, in order to enhance storage and handling.
  • the package is packed in an appropriate amount (for example, about 5 g) in a bag made of a breathable film such as a foamed film, and the package is sealed in a film having an appropriate gas barrier property such as a polyolefin film. It is recommended that the film be transported and opened before use, and the type of nonwoven fabric or breathable film used is not particularly limited.
  • Non-woven fabrics such as ordinary vegetable fibers, animal fibers, regenerated fibers, synthetic fibers, or various other materials that allow the passage of water vapor or vaporized gas while preventing leakage of vaporizable solid protective agents such as tablets Continuous foam sheet of resin And perforated films can all be used.
  • the vaporizable solid protective agent of the present invention contains, as active ingredients, at least three kinds of organic and / or inorganic nitrites, a water-retaining auxiliary and an acid substance, and preferably contains this.
  • a nonwoven fabric or a breathable film, etc. as will be evident in the examples described later, an excellent protective effect against the oxidatively corrosive metal material can be exhibited both in the initial stage and in the long period.
  • a protective agent can be obtained.
  • the vaporizable solid inhibitor of the present invention decomposes and vaporizes only after absorbing an appropriate amount of water and then dissolving the acid substance into acidic water. Example in which the loss of active ingredient does not occur even without moisture management and the production, packaging and storage can be simplified.
  • Dicyclohexylamine nitrite, a water-retaining auxiliary and an acid substance were blended in the ratio (mass ratio) shown in Table 1 below, and 0.5 g of the mixture was sealed and packed in a non-woven fabric. about 1 7 had location to adjust the room. 5
  • place 200 ml of 35% glycerin water in the box set the relative humidity in the box to 90% RH, and add 10 ml of 35% glycerin water to the inside diameter.
  • Nos. 1 to 11 are examples satisfying the requirements of the present invention
  • No. 12 is a known vaporizable solid inhibitor currently on the market, which is dicyclohexylamine. Nitrate 100% Powder.
  • No. 13 is a known vaporizable solid inhibitor currently on the market, which is a powder mixture of 80% dicyclohexylamine nitrite and 20% diisopropylamine nitrite.
  • No. 14 to 20 lack some of the requirements defined in the present invention.
  • No. 1 to: L1 satisfying the requirements of the present invention are all superior to No. 12 and 17 to 20.
  • No. 12 has a low amount of nitrite both in the initial stage and in the long term, and it is necessary to suspend the protective agent at intervals of 30 cm in order to expect a protective effect in a large capacity.
  • No. 13 has a high initial amount of nitrite and good results in the prevention test, but is capable of producing diisopropyl-N-nitrosoamine, which has been pointed out to be carcinogenic. Practicality is lacking due to the use of diisopropylamine nitrite, which has toxic properties.
  • No. 14 to 16 have a large initial amount of nitrous acid and good prevention test results, but have a long-term reduced amount of nitrous acid and have a long capacity to exhibit a protective effect with large capacity. And it is necessary to suspend a large number of protective agents.
  • No. 17 to 20 with no acid substance has a low nitrite content and poor protection ability in both the initial and long term.
  • Examples No. 1 to 11 which satisfy the requirements of the present invention, a large amount of gas is generated over a long period of time, so that excellent protection is obtained even at a distance of 2 m from the protection agent. It shows a positive effect and makes the process of prevention treatment simple.
  • the protective agent with N0.3 exhibited an inhibitory effect in 1 hour similarly to No. 13 which is a known immediate-acting inhibitor, and exhibited excellent immediate-inhibiting effect even after exposure.
  • No. 13 deteriorates its immediate effect after exposure and shows only a delayed effect.
  • the present invention is constituted as described above, and is characterized in that at least three kinds of organic and / or inorganic nitrite, a water-retaining auxiliary agent and an acid substance are mixed in a suitable ratio as active ingredients. Even when relatively simple manufacturing conditions and packaging are adopted, it is possible to provide a vaporizable solid protective agent that exhibits excellent protective performance under a dry atmosphere and a humid atmosphere, or in a short term or a long term. It has become.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)

Abstract

L'invention concerne un inhibiteur de corrosion solide et volatil comprenant un nitrite organique ou inorganique, un agent auxiliaire ayant des caractéristiques de rétention d'eau et/ou de libération d'eau durable, et une substance acide comme principes actifs. L'inhibiteur de corrosion solide et volatil fait preuve d'excellentes capacités de performances pour l'inhibition de la corrosion lors de l'inhibition de corrosion initiale, à long terme et/ou longue distance. L'inhibiteur ne présente pas de risque d'atteinte à la santé et fait preuve de capacités de performances excellentes pour l'inhibition de la corrosion même dans des conditions de fortes températures et de forte hygrométrie. La corrosion peut alors avoir lieu et peut supprimer considérablement la contamination d'un article que l'on doit protéger de la corrosion.
PCT/JP2003/000297 2002-01-16 2003-01-16 Inhibiteur de corrosion solide et volatil WO2003060197A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2002-7849 2002-01-16
JP2002007849A JP4149708B2 (ja) 2002-01-16 2002-01-16 気化性固形防錆剤

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WO2003060197A1 true WO2003060197A1 (fr) 2003-07-24

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004108991A1 (fr) * 2003-06-03 2004-12-16 Northern Technologies International Corporation Composition anticorrosion et article contenant ladite composition
US7261839B2 (en) 2002-01-22 2007-08-28 Northern Technologies International Corp. Tarnish inhibiting composition and article containing it
US8008373B2 (en) 2002-01-22 2011-08-30 Northern Technologies International Corp. Biodegradable polymer masterbatch, and a composition derived therefrom having improved physical properties

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4818693B2 (ja) * 2004-11-17 2011-11-16 三菱瓦斯化学株式会社 防錆剤
CN110885485A (zh) * 2019-11-20 2020-03-17 道伯(上海)包装材料有限公司 一种气化性防锈母粒及其制备方法和应用

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61147887A (ja) * 1984-12-18 1986-07-05 Rengo Co Ltd 防錆剤

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58512B2 (ja) * 1973-06-23 1983-01-06 ニホンカコウセイシ カブシキガイシヤ 気化性防錆剤
JPH073477A (ja) * 1993-06-21 1995-01-06 Nippon Kakoh Seishi Kk 防錆材料
JP3659765B2 (ja) * 1997-05-20 2005-06-15 株式会社キレスト技研 金属防食用組成物
JP4145990B2 (ja) * 1998-05-06 2008-09-03 株式会社キレスト技研 気化性金属防錆用組成物
JP4347458B2 (ja) * 1999-07-21 2009-10-21 キレスト株式会社 気化性防錆剤

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61147887A (ja) * 1984-12-18 1986-07-05 Rengo Co Ltd 防錆剤

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7261839B2 (en) 2002-01-22 2007-08-28 Northern Technologies International Corp. Tarnish inhibiting composition and article containing it
US7270775B2 (en) 2002-01-22 2007-09-18 Northern Technologies International Corp. Corrosion inhibiting composition and article containing it
US8008373B2 (en) 2002-01-22 2011-08-30 Northern Technologies International Corp. Biodegradable polymer masterbatch, and a composition derived therefrom having improved physical properties
WO2004108991A1 (fr) * 2003-06-03 2004-12-16 Northern Technologies International Corporation Composition anticorrosion et article contenant ladite composition

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JP4149708B2 (ja) 2008-09-17
JP2003213462A (ja) 2003-07-30

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