JP4818693B2 - anti-rust - Google Patents

Description

  The present invention relates to a rust preventive agent and a rust preventive method for metal materials during storage.

  As a method of preventing rusting due to condensation during storage of metal members, a method of sealing and wrapping metal members with a desiccant, a method of packaging with wrapping paper impregnated with a vaporizable rust inhibitor, or a vaporizable rust inhibitor can be used. There is a method of packaging with a packaging resin (film) contained (see Patent Document 1). There is also a method of replacing the inside of the metal member storage container with an inert gas. The method using a desiccant cannot prevent rusting even if it is completely dehumidified, and further rusts because oxygen and moisture permeate from the packaging material over time.

  The conventional method of using a wrapping paper impregnated with a vaporizable rust inhibitor such as dicyclohexylammonium nitrite takes time until the rust inhibitor vaporizes and exerts a rust preventive effect, and the rust inhibitor component is a metal. Since it adheres to the surface of the member, the cleanliness of the surface of the metal member is significantly lowered and cannot be used for storing precision parts. The method using a packaging resin (film) containing a vaporizable rust preventive agent is packaging because the vaporizable rust preventive agent volatilizes during the production of the packaging resin and the vaporizable rust preventive agent contained in the resin is difficult to vaporize. Rust prevention effect is not enough.

Inert gas replacement with nitrogen or argon is not easy to completely replace oxygen in the storage container, and oxygen and moisture permeate from the container material over time even after complete replacement. Rust occurs. From the above, in the conventional method, since the rusting cannot be prevented while keeping the surface of the metal member clean during long-term storage of the metal member, a solution method has been strongly demanded.
JP 2003-213462 A

  An object of the present invention is to provide a rust inhibitor and a rust prevention method for preventing rusting while keeping a metal member surface clean during long-term storage of the metal member.

 The inventors of the present invention sealed and stored a metal member surface together with a metal member as a rust preventive package by using a hydroxylamine compound or a hydrazine compound as an essential component and held in a water absorbent resin in a gas barrier container. The present invention was completed by finding that rusting can be prevented while keeping clean.

That is, the present invention
1. A rust inhibitor containing a hydroxylamine compound represented by the following formula (1) or a hydrazine compound represented by the following formula (2) and a water-absorbing resin;
2. 2. a package in which the rust preventive according to 1 is packaged with a breathable material; A rust prevention method characterized by storing a metal member in a gas barrier container together with the package according to 2 above,
It is about.

（式（１）中Ｒ^１、Ｒ^２、Ｒ^３は、それぞれ水素、炭素数１〜６のアルキル基、または炭素数２〜４のアルケニル基であり、これらの基は置換基を有しても良い。

(In Formula (1), R ¹ , R ² and R ³ are each hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkenyl group having 2 to 4 carbon atoms, and these groups have a substituent. Also good.

（式（２）中Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４は、それぞれ水素、炭素数１〜６のアルキル基、または炭素数２〜４のアルケニル基であり、これらの基は置換基を有しても良い。）

(In the formula (2), R ¹ , R ² , R ³ and R ⁴ are each hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkenyl group having 2 to 4 carbon atoms, and these groups have substituents. You may have.)

The metal rust preventive agent of the present invention has an excellent effect of suppressing rust generated by dew condensation during long-term storage, and the metal surface is clean, so it is cleaned when performing metal processing (plating, painting, etc.) after storage. Since steps (rust removal, metal surface cleaning treatment, etc.) can be omitted, time and chemical cost can be reduced.

  The metal targeted by the rust preventive agent of the present invention is mainly iron, but other than these, grinding copper, nickel, chromium, cobalt, lead, zinc, aluminum, titanium, tin, gold, silver, etc. and alloys thereof・ Applicable to cutting, die casting and sintering. Furthermore, the present invention can be applied to products that are metallized by means of adhesion, pressure bonding, plating, vapor deposition, ion plating, or the like on the surface of resin, glass, ceramics or the like.

  Specific examples of preferred hydroxylamine compounds represented by the formula (1) include hydroxylamine, O-methylhydroxylamine, O-ethylhydroxylamine, N-methylhydroxylamine, N, N-dimethylhydroxylamine, N, O-dimethylhydroxylamine, N-ethylhydroxylamine, N, N-diethylhydroxylamine, N, O-diethylhydroxylamine, O, N, N-trimethylhydroxylamine, N- (2-methoxyethyl) hydroxylamine N-allylhydroxylamine, N, O-diallylhydroxylamine, O-cyclohexyl-N, N-dimethylhydroxylamine and the like. Of these, hydroxylamine and N, N-diethylhydroxylamine are the most suitable.

  Specific examples of preferred hydrazine compounds represented by formula (2) are hydrazine, methyl hydrazine, ethyl hydrazine, 1,1-dimethyl hydrazine, 1,2-dimethyl hydrazine, 1,1-diethyl hydrazine, 1 , 2-diethylhydrazine, isopropylhydrazine, 1,2-diisopropylhydrazine, cyclohexylhydrazine, allylhydrazine and the like. Of these, hydrazine, methyl hydrazine, 1,1-dimethylhydrazine, 1,2-dimethylhydrazine, ethylhydrazine, 1,1-diethylhydrazine, and 1,2-diethylhydrazine are most suitable.

  The concentration of the hydroxylamine compound or hydrazine compound is preferably 0.001 to 50% by weight, more preferably 0.05 to 30% by weight, and particularly preferably 0.5 to 30% by weight. If it is less than 0.001% by weight, the rust prevention effect is insufficient, and if it exceeds 50% by weight, no further rust prevention effect can be obtained.

  In the present invention, when an immediate effect of rust prevention is required, it is preferable to hold a composition in which acetylene alcohol is further added to a hydroxylamine compound or a hydrazine compound in a water absorbent resin. Examples of acetylene alcohols include 1-propyn-3-ol, 1-butyn-3-ol, 1-butyn-4-ol, 2-butyn-1-ol, 3-methyl-1-butyn-3-ol, 3 -Methyl-1-butyn-4-ol, 1-pentyn-3-ol, 3-methyl-1-pentyn-3-ol, 1-hexyn-3-ol, 3,5-dimethyl-1-hexyne-3 -Ol, 1-ethynylcyclohexanol, 1-heptin-3-ol, 1-octin-3-ol, 1-nonin-3-ol, 1-decyn-3-ol, 2-butyne-1,4-diol Acetylene alcohol having 3 to 10 carbon atoms such as 3-hexyne-2,5-diol, 3,5-dimethyl-3-hexyne-2,5-diol, 4-ethyl-1-octin-3-ol and the like is preferable. And Among these, 3-methyl-1-pentin-3-ol (methylpentynol), 3-methyl-1-butyn-3-ol (methylbutynol), 3,5-dimethyl-1-hexyne-3 -Ol (dimethylhexynol), 1-ethynylcyclohexanol and the like are optimal. In the rust inhibitor of the present invention, the concentration of acetylene alcohol is preferably 0.001 to 50% by weight, more preferably 0.01 to 10% by weight, and particularly preferably 0.1 to 10% by weight. If it is less than 0.001% by weight, the rust prevention effect is insufficient, and if it exceeds 50% by weight, no further rust prevention effect can be obtained.

  The water-absorbent resin of the present invention is made of a polymer having a crystal structure or a crosslinked structure in the polymer, so that it can quickly absorb and swell when contacted with water. Specifically, polyvinyl alcohol, poly (meth) acrylate, poly (meth) acrylamide, polysulfonate, polyethylene oxide, carboxymethylcellulose, acrylate and acrylate copolymer, vinyl acetate and acrylate copolymer Examples thereof include hydrolysates of coalesced starch and acrylic acid graft polymer. Preferably, a hydrophilic epoxy resin (a) having two or more epoxy groups in one molecule and an amine compound (b) having two or more primary or secondary amino groups in one molecule are essential components. These are cured resins obtained by reacting them.

  The epoxy resin (a) is not particularly limited as long as it is a hydrophilic compound having at least two epoxy groups in one molecule. Specifically, polyether-type epoxy resin obtained from the reaction of ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol and the like with epichlorohydrin, glycerin, polyglycerol, trimethylolpropane, sorbitol and the like and epichlorohydrin And polyhydric alcohol type epoxy resins obtained from the above reaction. Of these, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerol polyglycidyl ether, polyglycerol polyglycidyl ether and mixtures thereof are optimal. The epoxy equivalent of the epoxy resin is preferably 130 to 1500 g / eq, and more preferably 200 to 1000 g / eq.

  Further, the amine compound (b) is not particularly limited as long as it is a compound having at least two primary or secondary amino groups in one molecule. Specifically, ethylenediamine, polyethylenediamine, Aliphatic primary amines such as polyether diamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, xylylenediamine, alicyclic primary amines such as bisaminomethylcyclohexane, isophoronediamine, metaphenylenediamine, diamino Aliphatic primary amines such as aromatic primary amines such as diphenylmethane, ethylene oxide adducts such as ethylenediamine, polyethylenediamine, polyetherdiamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and xylylenediamine Grade amines, bis aminomethyl cyclohexane, alicyclic secondary amines such as the ethylene oxide adduct of isophorone diamine, piperazine, dicyandiamide, and the like. Of these, polyethylene diamine, polyether diamine, xylylenediamine, bisaminomethylcyclohexane, and isophorone diamine are most suitable.

  The ratio of the amine compound (b) to the epoxy resin (a) of the water-absorbent resin is an equivalent ratio of the epoxy group of the epoxy resin (a) to the hydrogen atom directly bonded to the nitrogen atom of the amine compound (b) (epoxy equivalent: The active hydrogen equivalent) is preferably from 1: 0.3 to 1: 3, more preferably from 1: 0.6 to 1: 2.5, particularly preferably from 1: 0.7 to 1: 2.2.

  The epoxy resin (a) and the amine compound (b) are cured by treating at 0 to 150 ° C. for 1 to 48 hours, preferably at 40 to 120 ° C. for 2 to 10 hours to obtain a water absorbent resin. At that time, a generally known curing accelerator can be added to adjust the curing rate. Examples thereof include tertiary amines, imidazoles and derivatives thereof.

  The method for retaining the essential component comprising the hydroxylamine compound or hydrazine compound of the present invention in the water-absorbent resin is not particularly limited, but the water-absorbent resin is pulverized to an appropriate size to obtain the hydroxylamine compound or hydrazine compound. It can hold | maintain by being immersed in aqueous solution at 5-100 degreeC for 0.5 to 72 hours.

The rust preventive agent by the water-absorbing resin holding the essential component comprising the hydroxylamine compound or hydrazine compound of the present invention has an air permeability of 1000 ml / m ² · day · atm or more at 25 ° C. and 60% RH. Used as a package packaged in a packaging material. The breathable packaging material and configuration are not particularly limited. For example, a breathable packaging material of a laminated material based on paper or non-woven fabric, a perforated plastic film or sheet, etc. is filled with a water-absorbing resin holding an essential component consisting of a hydroxylamine compound or a hydrazine compound, The package material is heat-sealed to form a package.

The rust inhibitor used as the package is sealed in a gas barrier container together with a metal to be stored. As the gas barrier container, a bag, a case, a can, or the like made of a gas barrier plastic or metal is used. Specific examples include a case made of a resin such as polyethylene, polypropylene, nylon, polyester, vinyl chloride, and polystyrene, or a bag of a laminated material made of a film or sheet such as polyethylene, polypropylene, nylon, or polyester. When the material is a plastic film or sheet, aluminum, silicon oxide, selenium oxide, or the like may be used by vapor deposition on the surface in order to ensure gas barrier properties. Moreover, the metal can which consists of iron, aluminum, stainless steel etc. is also mentioned. The gas barrier container preferably has an oxygen permeability at 25 ° C. and 60% RH of 50 ml / m ² · day · atm or less, and a water vapor permeability at 40 ° C. and 90% RH of 5 g / m ² · day or less. More preferably, the oxygen permeability at 25 ° C. and 60% RH is 10 ml / m ² · day · atm or less, and the water vapor permeability at 40 ° C. and 90% RH is 1 g / m ² · day or less.

  EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but is not limited to the following examples.

Example 1
82 parts of polyethylene glycol diglycidyl ether (Denacol EX-841 manufactured by Nagase Kasei Co., Ltd., epoxy equivalent: 370 g / eq) preheated to 60 ° C. and glycerol polyglycidyl ether (Denacol EX-313 manufactured by Nagase Kasei Co., Ltd.) 2 parts of epoxy equivalent: 141 g / eq) were put into a 500 ml beaker, and 0.1 part of benzyldimethylamine was further added as a curing accelerator and mixed and stirred. To this, 16 parts of metaxylenediamine (active hydrogen equivalent: 34 g / eq) was added and further stirred. This mixed solution was poured into an aluminum mold, heated in a dryer at 80 ° C. for 1 hour, further heated to 120 ° C. and heated for 1 hour to obtain a cured resin. The cured resin was pulverized in a mortar, and 3 g of this pulverized product was immersed in 100 ml of a 5 wt% aqueous hydroxylamine solution at 25 ° C. for 24 hours. Next, this hydroxylamine-containing resin cured product is filled into a breathable packaging material (inner size 80 mm × 50 mm) made of a paper / polyethylene film laminate, and the peripheral portion is heat-sealed with the polyethylene film surface inward to prevent rust. An agent package was produced. The rust preventive package was subjected to a vaporizable rust prevention test. After the test (according to JIS-Z-1519), the state of occurrence of rust on the test piece was visually observed and evaluated in three stages according to the following criteria. The results are shown in Table 1.
○ No rust generated △ Rust generated on less than 50% surface area of test piece × Rust generated on 50% or more surface area of test piece

Example 2
The same procedure as in Example 1 was conducted except that 5% by weight of hydrazine was used instead of 5% by weight of hydroxylamine. Table 1 shows the results of the vaporizable rust preventive test.

Example 3
The same procedure as in Example 1 was conducted except that 5 wt% N, N-diethylhydroxylamine was used instead of 5 wt% hydroxylamine. Table 1 shows the results of the vaporizable rust preventive test.

Example 4
The same procedure as in Example 1 was conducted except that 5% by weight methylhydrazine was used instead of 5% by weight hydroxylamine. Table 1 shows the results of the vaporizable rust preventive test.

Example 5
The same procedure as in Example 1 was carried out except that 5 wt% ethylhydrazine was used instead of 5 wt% hydroxylamine. Table 1 shows the results of the vaporizable rust preventive test.

Example 6
The same procedure as in Example 1 was conducted except that 5 wt% 1,1-dimethylhydrazine was used instead of 5 wt% hydroxylamine. Table 1 shows the results of the vaporizable rust preventive test.

Example 7
The same procedure as in Example 1 was conducted except that 5% by weight of 1,2-dimethylhydrazine was used instead of 5% by weight of hydroxylamine. Table 1 shows the results of the vaporizable rust preventive test.

Example 8
Instead of adding 82 parts of polyethylene glycol diglycidyl ether (Denacol EX-841), 2 parts of glycerol polyglycidyl ether and 16 parts of metaxylenediamine, an epoxy equivalent of polyethylene glycol diglycidyl ether (Denacol EX-861 manufactured by Nagase Chemical Co., Ltd.) 551 g / eq) The same procedure as in Example 1 except that 91.5 parts and 8.5 parts of metaxylenediamine were added. Table 1 shows the results of the vaporizable rust preventive test.

Example 9
Instead of adding 82 parts of polyethylene glycol diglycidyl ether (Denacol EX-841), 2 parts of glycerol polyglycidyl ether, 0.1 part of benzyldimethylamine and 16 parts of metaxylenediamine, polyethylene glycol diglycidyl ether (Denacol EX-861) 86 parts, 8 parts of polypropylene glycol diglycidyl ether (EX-920 Nagase Kasei Co., Ltd., epoxy equivalent 176 g / eq), 1 part of benzyldimethylamine, 6 parts of isophoronediamine (active hydrogen equivalent 43 g / eq) Was carried out in the same manner as in Example 1. Table 1 shows the results of the vaporizable rust preventive test.

Example 10
Instead of adding 82 parts of polyethylene glycol diglycidyl ether (Denacol EX-841), 2 parts of glycerol polyglycidyl ether, 0.1 part of benzyldimethylamine and 16 parts of metaxylenediamine, polyethylene glycol diglycidyl ether (Denacol EX-861) The same procedure as in Example 1 was conducted except that 88.6 parts, 1 part of benzyldimethylamine, and 11.4 parts of 1,3-bisaminomethylcyclohexane (active hydrogen equivalent: 36 g / eq) were added. Table 1 shows the results of the vaporizable rust preventive test.

Example 11
Instead of 82 parts of polyethylene glycol diglycidyl ether (Denacol EX-841), 2 parts of glycerol polyglycidyl ether and 16 parts of metaxylenediamine, 88.3 parts of polyethylene glycol diglycidyl ether (Denacol EX-861), triethylenetetramine (Active hydrogen equivalent 37 g / eq) The same procedure as in Example 1 was performed except that 11.7 parts were added. Table 1 shows the results of the vaporizable rust preventive test.

Comparative Example 1
The same procedure as in Example 1 was performed except that pure water was used instead of the hydroxylamine aqueous solution. Table 1 shows the results of the vaporizable rust preventive test.

Comparative Example 2
The same procedure as in Example 1 was performed except that 5 g of silica gel was used instead of the water absorbent resin. Table 1 shows the results of the vaporizable rust preventive test.

Comparative Example 3
It carried out similarly to Example 1 except having used activated carbon 5g instead of using a water absorbing resin. Table 1 shows the results of the vaporizable rust preventive test.

Example 12
88.3 parts of polyethylene glycol diglycidyl ether (Denacol EX-861 manufactured by Nagase Kasei Co., Ltd., epoxy equivalent: 551 g / eq) was collected in a 500 ml beaker, 100 parts of ion-exchanged water was added thereto, and the mixture was stirred at 60 ° C. did. To this, 11.7 parts of triethylenetetramine (active hydrogen equivalent: 37 g / eq) was added and further stirred. This was heated in a dryer at 80 ° C. for 2 hours to obtain a cured resin. The cured resin was pulverized in a mortar, and 5 g of the pulverized product was immersed in 100 ml of an aqueous solution of 1% by weight 1,1-diethylhydrazine and 0.1% by weight methylpentinol at 25 ° C. for 5 hours. Using this immersed resin cured product, a rust preventive package was produced in the same manner as in Example 1 and a vaporizable rust preventive test was conducted. The results are shown in Table 1.

Example 13
The same procedure as in Example 12 was performed except that 0.1 wt% methylbutynol was used instead of 0.1 wt% methylpentinol. Table 1 shows the results of the vaporizable rust preventive test.

Example 14
60 parts of polyethylene glycol diglycidyl ether (Denacol EX-861 manufactured by Nagase Kasei Co., Ltd., epoxy equivalent: 551 g / eq) was collected in a 500 ml beaker, and 0.2 parts of benzyldimethylamine and 100 parts of ion-exchanged water were added thereto. The mixture was stirred. To this, 40 parts of polyetheramine (active hydrogen equivalent: 500 g / eq) was added and further stirred. This was heated in a dryer at 80 ° C. for 2 hours, further heated to 90 ° C. and heated for 3 hours to obtain a cured resin. The cured resin was pulverized in a mortar, and 5 g of the pulverized product was immersed in 100 ml of an aqueous solution of 1% by weight 1,2-diethylhydrazine and 0.1% by weight dimethylhexinol at 25 ° C. for 5 hours. Using this immersed resin cured product, a rust preventive package was produced in the same manner as in Example 1 and a vaporizable rust preventive test was conducted. The results are shown in Table 1.

Example 15
The same procedure as in Example 14 was performed except that 0.1 wt% 1-ethynylcyclohexanol was used instead of 0.1 wt% dimethylhexinol. Table 1 shows the results of the vaporizable rust preventive test.

Claims (1)

Containing hydroxylamine, hydrophilic epoxy resin (a) having two or more epoxy groups in one molecule, and amine compound (b) having two or more primary or secondary amino groups in one molecule it contains a water-absorbent resin is a cured resin obtained by reacting a rust agent characterized the,
The hydrophilic epoxy resin (a) is at least one selected from the group consisting of polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerol polyglycidyl ether and polyglycerol polyglycidyl ether;
A rust inhibitor, wherein the amine compound (b) is at least one selected from the group consisting of polyethylene diamine, polyether diamine, xylylenediamine, bisaminomethylcyclohexane and isophoronediamine .