WO1999057333A1 - Composition antirouille vaporisable pour metaux - Google Patents

Composition antirouille vaporisable pour metaux Download PDF

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Publication number
WO1999057333A1
WO1999057333A1 PCT/JP1999/002165 JP9902165W WO9957333A1 WO 1999057333 A1 WO1999057333 A1 WO 1999057333A1 JP 9902165 W JP9902165 W JP 9902165W WO 9957333 A1 WO9957333 A1 WO 9957333A1
Authority
WO
WIPO (PCT)
Prior art keywords
water
composition
ammonium
nitrite
water retention
Prior art date
Application number
PCT/JP1999/002165
Other languages
English (en)
Japanese (ja)
Inventor
Nobuyoshi Nambu
Kazuhiko Fukuda
Qun Zheng
Original Assignee
Chelest Giken Co., Ltd.
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 Chelest Giken Co., Ltd. filed Critical Chelest Giken Co., Ltd.
Publication of WO1999057333A1 publication Critical patent/WO1999057333A1/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 composition for protecting a vaporizable metal, for example, whether the metal is susceptible to oxidation such as various mechanical parts and automobile parts made of steel materials.
  • a composition for metal barriers to prevent the surface from being oxidized and emitted especially in the short and long term
  • the present invention relates to a vaporizable metal protective composition which exhibits excellent anti-mirror properties and can be easily removed from the surface of a promotional component after use.
  • Background Art As described above, the most widely used countermeasures against metal materials as described above have been to apply a metal oil to the surface of a metal member to be protected to form an oil film.
  • VCI Volatile Co Rrosion Inhibitor
  • a typical example is a sublimable cyclohexylammonium cyclocanolenomate.
  • C H C has a vapor pressure of 4 x l O _lmm H g (2
  • the temperature is as high as 5 ° C, which is excellent for initial bell protection.
  • the packaging must be strictly designed for long-term protection.
  • the vapor pressure of DICAN is as low as 1 XI 0 -4 mm Hg (25 ° C), and it takes more than 20 hours to exhibit the protection effect. It lacks the initial defense server.
  • vapor pressure of DIPAN is 5 x lO—3 mmHg (2
  • the present invention has been made in view of the above-mentioned circumstances, and has a purpose of being a vaporizable anti-honey agent which is excellent in both initial promotion ability and long-term protection ability. And without any health problems. Is a vaporizable metal anti-foaming composition that exhibits excellent mackerel protection under hot and humid conditions, where sales are likely to occur, and that can be easily removed from products to be protected after use. They are trying to provide them.
  • nitrite constituting the composition for preventing metal from vaporization of the present invention a water-soluble nitrite represented by the following formula [1] is exemplified as a preferable one, and these are used alone. In addition to being able to be used, two or more kinds can be used in combination as needed.
  • R 1, 2 and R 3 are the same or different and each represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group or an alkanol group). And at least one group represents an alkyl group, a cycloalkyl group, an alkenyl group or an alkanol group)
  • dicyclohexylamine nitrite particularly preferred is dicyclohexylamine nitrite.
  • ammonium salts include boric acid, phosphoric acid, carbonate and the like.
  • ammonium salts of organic carboxylic acids and more specifically, water-soluble ammonium salts represented by the following formulas [2], [3] and [4] are preferred. These may be used alone, or two or more of them may be used in combination.
  • R 4 represents a hydrogen atom or a monovalent hydrocarbon group which may have a substituent.
  • R 5 represents a divalent hydrocarbon group which may have a substituent.
  • ammonium salts particularly preferred are ammonium benzoate, ammonium salicylate, and ammonium p-nitrobenzoate.
  • water retention or water sustained release auxiliary agent those having a water retention ratio of 0.03 to 1.0 times obtained by the following method are preferred.
  • the content of the ammonium salt is 1 to 20 mol with respect to 100 mol of the nitrite, and the content of the water-retaining fiber is defined as the content of the ammonium salt.
  • the vaporizable metal is extremely excellent in both the initial honing prevention ability and the long-term protection ability. It becomes a composition for promotion.
  • BEST MODE FOR CARRYING OUT THE INVENTION As described above, in the present invention, one or more kinds of organic amine nitrite (hereinafter, sometimes referred to as “A component”) and an inorganic or organic compound are used.
  • ammonium salts of boric acid, phosphoric acid, carbonic acid and organic carboxylic acid are preferred as the B component.
  • ammonium borate salts there are ammonium metaborate, ammonium orthoborate, ammonium tetraborate, etc., among which are particularly preferred.
  • ammonium tetraborate salt examples include mono-ammonium phosphate, di-ammonium phosphate, and tri-ammonium phosphate, with preference given to di-ammonium phosphate and tri-ammonium phosphate. It is an ammonia.
  • ammonium carbonate diammonium carbonate and monoammonium carbonate are both preferably used.
  • ammonium salts the most preferred in the present invention are ammonium carbonate, ammonium benzoate, ammonium salicylate, and ammonium P-nitrobenzoate. And ammonium benzoate, and benzoic acid ammonium is recommended as the most preferred ammonium salt.
  • ammonium salts may be used alone, or may be used in an appropriate combination of two or more as needed.
  • a water-retaining or water-releasing release aid it has the property of retaining an appropriate amount of water necessary for the hydrolysis or releasing it little by little as described later in detail.
  • Any substance can be used as long as it has the above-mentioned moderate water retention ratio, and it is particularly preferable that it can be easily obtained at low cost.
  • It is a fiber substance. Examples of the type thereof include animal fiber, vegetable fiber, regenerated fiber, and synthetic fiber, such as wool, cotton, hemp, cellulose, viscose rayon, and the like. Among them, cellulose fiber is particularly preferred. These fibers have an important function in promoting the hydrolysis reaction of the nitrite and ammonium salt of the organic amino compound by appropriately absorbing moisture in the atmosphere during use as described below.
  • the water retention ratio obtained by the above method is 0.03 to 1.0. It is better to select and use 0 times, more preferably 0.05 to 0.3 times.
  • the metal basin action exerted by the components A and B and the water-retaining fiber can be explained as follows.
  • a hydrolysis reaction represented by the formula is caused to produce ammonium nitrite having a high vapor pressure at room temperature and an excellent protection effect.
  • the A and B components and the hydrolysis effect due to the presence of water that is appropriately retained or released by the water retention or water sustained release auxiliary are used. Therefore, they exhibit excellent effects in all of the initial protective properties, the long-term protective properties, and the protective properties under high temperature and high humidity. If even one of these components is not sufficient, the present invention is used. so It is not possible to achieve the intended high level of promotional effects.
  • the amount of the component B is more preferably 1 mol or more with respect to 100 mol of the component A.
  • the amount is preferably not less than 5 mol and not more than 20 mol, more preferably not more than 15 mol.
  • the amount of the B component is insufficient, nitrite by hydrolysis is used. Insufficient amount of ammonia is produced, resulting in a shortage of initial promotion ability.
  • the amount of component B is too large, the consumption of component A due to hydrolysis increases. It tends to be insufficient for long-term honing.
  • the amount of the water retention agent or water sustained release auxiliary can be selected from a wide range according to the water retention ratio, but as a general standard, 1 part by weight or more, more preferably 2 parts by weight or more and 100000 parts by weight or less, more preferably 100 parts by weight with respect to 100 parts by weight of the total of the above components A and B. If the amount of the auxiliary agent is insufficient, the hydrolysis reaction tends to be insufficient due to insufficient water retention, making it difficult to obtain a sufficient initial promotion effect. On the other hand, if the amount is too large, the water retention becomes too large, and the hydrolysis is completed within a short time, and it is difficult to sufficiently exert the long-term anti-housing effect.
  • the above-mentioned components A and B are used in the above-mentioned suitable compounding ratio, and further, a powdery water-retaining or water-releasing auxiliary agent is used.
  • a powdery water-retaining or water-releasing auxiliary agent is used.
  • the above A and B components in an amount of preferably 2.5 to 10 parts by weight with respect to 100 parts by weight of the above components A and B, and used as a powder or in the form of tablets or tablets. Used as granules Is received.
  • the above components A and B are used in the above-mentioned suitable mixing ratio, and are preferably 1 to 25% by weight, more generally 5 to 10% by weight, such as alcohol. It is dissolved in a harmless organic solvent and impregnated into fibers such as woven, knitted, non-woven, string, etc. used as a water-retaining or water-releasing auxiliary agent. Is used after being volatilized.
  • the water retained by the water-retaining or sustained-release aid is utilized, and the hydrolysis effect of the component A and the component B is fully utilized.
  • a vaporizable protection composition that has both initial protection performance and long-term protection performance and exhibits excellent protection performance even in a humid atmosphere.
  • the present invention will be described in more detail with reference to examples. However, the present invention is not limited by the following examples, and has the purport of the preceding and the following. It is also possible to carry out the present invention with appropriate modifications within a range that is compatible with the above, and all of them are included in the technical scope of the present invention.
  • the water retention ratio determined by the above method for the fibers used as the water retention agent or water sustained release auxiliary in the experiment is as follows. In the case of powders and tablets, 0.05 g was used, and the protective agent impregnated in the fiber cloth was used so that the amount of the protective component was 0.05 g, and evaluated according to the following criteria.
  • Acrylic fiber 0.01 times
  • Example 1 DICHAN 85% 7monium carbonate 10% Cell D-source 5% powder ⁇
  • Example 2 DICHAN 85% benzoic acid finished 10% cell ⁇ -source 5% powder ⁇
  • Example 3 DICHAN 85% 7% benzoic acid 10 % Cell mouth 5% Tablet ⁇
  • Example 4 DICHAN 9% Benzoic acid ammonium 1% Cell mouth 90% plate ⁇
  • Example 5 DICHAN 85% Cell ammonium phosphate 10% Cell space 5% Powder ⁇
  • Comparative Example 1 DICHAN 100% Powder X Comparative Example 2 DICHAN 95% Cell Space 5% Powder X Comparative Example 3 DICHAN 95% Cell mouth 5% Tablet X Comparative Example 4
  • DICHAN 90% Benzoic Acid 7% Monium 10% Powder ⁇ Comparative Example 5 DICHAN 90% Benzoic acid t Nidium 10% Tablet ⁇ Comparative Example 6 CHC 100% Powder X Comparative Example 7 DICHAN 85% Benzoic acid ⁇ monium 10% Water absorbent resin 5% Powder ⁇ Comparative Example 8 DICHAN 85 % Benzoic acid 7% Mon
  • Comparative Example 7 is an example in which a water-absorbing resin having a high water retention ratio was used, and hydrolysis of the anti-foam component progressed in the early stage of use, and a satisfactory promotional effect was not obtained. Further, Comparative Example 8 is an example in which a synthetic fiber having almost no water retention was used, and it was still unsatisfactory and no anti-housing effect was expected.
  • Table 3 below shows the results obtained by examining the effective reaching distance of the bellproof component in the height direction. The test was performed by the following method.
  • a hot rolled steel plate (SS-41, 45mm x 45mm x 8mm) polished with 240 # polishing cloth is placed 19cm from the bottom of a 30cm x 30cm x 180cm acrylic resin container (162 liters). Suspended in the height direction at an interval of 5 g, and 5 g of powdered fireproofing agent on the bottom (in the case of a honeyproofing agent impregnated in water-retaining fiber cloth, the amount of the waterproofing component is 5 g) ), And cover with a lid and seal with gum tape. After leaving the entire container in a room at 20 ° C for one month, The presence or absence of occurrence is visually evaluated according to the following criteria.
  • Examples 1 to 5 are examples satisfying the requirements of the present invention, and Comparative Examples 1 to 6 do not contain one or two components of the above examples.
  • This is a comparative example.
  • the examples containing the three components all have excellent anti-housing ability as compared with the comparative examples.
  • the present invention is constituted as described above, and is composed of A and B components and water retention.
  • a water-release sustaining aid is contained as an essential component, and preferably, by blending each of the components in the above-mentioned suitable ratio, the anti-propellant which volatilizes from those substances is obtained.
  • a protective composition showing excellent mackerel performance in a gas-phase atmosphere.
  • this composition exhibits an excellent anti-protective action in both initial and long-term anti-foaming compared to conventional vaporizable anti-foaming agents, and also has an excellent anti-bacterial action even in a high humidity atmosphere. Demonstrate.
  • the composition exerts an excellent protective effect in the form of a powder, and also impregnates tablets or granules or fibers or fibers such as paper or cloth to volatilize vaporizable components. By doing so, it is possible to exert a protective effect, and it can be widely used in various forms depending on the application.

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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

Composition antirouille vaporisable pour métaux, qui possède d'excellentes performances de protection contre la rouille aussi bien à court qu'à long terme, qui n'est pas nocive pour la santé, qui confère une protection contre la rouille très efficace, même dans les atmosphères très humides et très chaudes où le phénomène de rouille est susceptible de se produire, et qui, après usage, est facile à enlever du produit protégé contre la rouille. La composition comprend le sel d'acide nitreux d'une amine organique, au moins un sel d'ammonium d'acide inorganique ou un sel d'ammonium d'acide organique, et un agent de rétention d'eau ou de libération contrôlée d'eau, qui de préférence a un rapport de rétention d'eau compris entre 0,03 et 1,0 suivant la méthode exposée dans la description.
PCT/JP1999/002165 1998-05-06 1999-04-22 Composition antirouille vaporisable pour metaux WO1999057333A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP12364998A JP4145990B2 (ja) 1998-05-06 1998-05-06 気化性金属防錆用組成物
JP10/123649 1998-05-06

Publications (1)

Publication Number Publication Date
WO1999057333A1 true WO1999057333A1 (fr) 1999-11-11

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WO (1) WO1999057333A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1320164C (zh) * 2003-10-22 2007-06-06 北京化工大学 用于工业设备保护的气相缓蚀剂及其制备方法

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4149708B2 (ja) * 2002-01-16 2008-09-17 中部キレスト株式会社 気化性固形防錆剤
CN107419273A (zh) * 2017-06-28 2017-12-01 常州凯恒纺织品有限公司 一种水基防锈剂及其制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS599180A (ja) * 1982-07-08 1984-01-18 Chiyoda Kagaku Kenkyusho:Kk 気化性の金属防錆剤
JPH01100286A (ja) * 1987-10-09 1989-04-18 Nitto Denko Corp 防錆用物品
JPH10317177A (ja) * 1997-05-20 1998-12-02 Kiresuto Giken:Kk 金属防食用組成物

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS599180A (ja) * 1982-07-08 1984-01-18 Chiyoda Kagaku Kenkyusho:Kk 気化性の金属防錆剤
JPH01100286A (ja) * 1987-10-09 1989-04-18 Nitto Denko Corp 防錆用物品
JPH10317177A (ja) * 1997-05-20 1998-12-02 Kiresuto Giken:Kk 金属防食用組成物

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1320164C (zh) * 2003-10-22 2007-06-06 北京化工大学 用于工业设备保护的气相缓蚀剂及其制备方法

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Publication number Publication date
JP4145990B2 (ja) 2008-09-03
JPH11315387A (ja) 1999-11-16

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