CN101052747B - Antirust agent - Google Patents

Antirust agent Download PDF

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Publication number
CN101052747B
CN101052747B CN2005800375459A CN200580037545A CN101052747B CN 101052747 B CN101052747 B CN 101052747B CN 2005800375459 A CN2005800375459 A CN 2005800375459A CN 200580037545 A CN200580037545 A CN 200580037545A CN 101052747 B CN101052747 B CN 101052747B
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Prior art keywords
rust
preventive agent
compound
hydrazine
formula
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CN2005800375459A
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Chinese (zh)
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CN101052747A (en
Inventor
高桥健一
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Mitsubishi Gas Chemical Co Inc
Ryoko Chemical Co Ltd
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Mitsubishi Gas Chemical Co Inc
Ryoko Chemical Co Ltd
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    • 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
    • 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
    • C09D5/086—Organic or non-macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0073—Anticorrosion compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen
    • C11D7/3209—Amines or imines with one to four nitrogen atoms; Quaternized amines
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen
    • C11D7/3218—Alkanolamines or alkanolimines
    • 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
    • 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
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/14—Nitrogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

Disclosed is an antirust agent for protecting the surface of a metal member from rust while maintaining the surface clean during long-time storage. Also disclosed is a method for preventing rust. Specifically disclosed is an antirust agent characterized by containing a hydroxylamine compound represented by the formula (1) below or a hydrazine compound represented by the formula (2) below and a water-absorbing resin. Also disclosed is an antirust obtained by wrapping the antirust agent with an air-permeable material. Further disclosed is a method for preventing rust which is characterized by storing a metal member in a gas-barrier container together with the wrapped antirust agent. In the formula (1) below, R<1>, R<2> and R<3> respectively represent a hydrogen atom, an alkyl group having 1-6 carbon atoms or an alkenyl group having 2-4 carbon atoms; and these groups may have a substituent. In the formula (2) below, R<1>, R<2>, R<3> and R<4> respectively represent a hydrogen atom, an alkyl group having 1-6 carbon atoms or an alkenyl group having 2-4 carbon atoms; and these groups may have a substituent.

Description

Rust-preventive agent
Technical field
The present invention relates to that the metallic substance in preserving is had good inhibition the get rusty rust-preventive agent and the rust-proofing method of effect.
Background technology
As the method that prevents of getting rusty that produces because of dewfall during metal parts is preserved, the method (with reference to patent documentation 1) that method that metal parts is packed with the seal-packed method of siccative, with the wrapping paper that is impregnated with dichan is arranged, pack with the packaging resin (film) that contains dichan.In addition, also has the method for the preservation internal tank of metal parts being used inert gas replacement.Utilize the method for siccative,, and pass in time, can see through oxygen and moisture and cause and get rusty from wrapping material even dehumidifying can not prevent to get rusty fully.
Usefulness in the past is impregnated with the method that the wrapping paper of dichans such as dicyclohexyl ammonium nitrate is packed, because rust-preventive agent gasification and performance rust-proof effect need the time, and the rust-preventive agent composition is attached to metal part surface, so the cleanliness factor of metal part surface significantly reduces, can not be used to preserve precise part etc.The method of packing with the packaging resin that contains dichan (film), owing to will volatilizing, dichan in the making processes of packaging resin lost efficacy, and the dichan that contains in the resin is difficult to gasification, so the rust-proof effect when packing is used is insufficient.
Come method of replacement with rare gas elementes such as nitrogen or argon gas, be not easy the oxygen of preserving in the container is replaced fully, even and displacement fully, process in time also can see through oxygen or moisture and causes and get rusty from wrapping material.Therefore,, when the prolonged preservation metal parts, can not keep the cleaning of metal part surface, and can not prevent to get rusty, so thirst for developing solution by above-mentioned method in the past.
Patent documentation 1: the spy opens the 2003-213462 communique
Summary of the invention
The invention provides the rust-preventive agent and the rust-proofing method that when the prolonged preservation metal parts, can keep the cleaning of metal part surface and prevent to get rusty.
The inventor finds, by in gas-barrier container, the rust-preventive agent wrapping body being sealed preservation with metal parts, can keep the cleaning of metal part surface and prevent to get rusty, finish the present invention thus, wherein above-mentioned rust-preventive agent wrapping body with hydroxylamine compound or hydrazine compound as must composition remaining on the absorbent resin and obtain.
Just, the present invention relates to
1, rust-preventive agent is characterized in that, this rust-preventive agent contains by the hydroxylamine compound of following formula (1) expression or hydrazine compound and the absorbent resin of being represented by following formula (2);
2, wrapping body, this wrapping body is packed above-mentioned 1 described rust-preventive agent and is obtained with poromeric material; And
3, rust-proofing method is characterized in that, metal parts is kept in the gas-barrier container with above-mentioned 2 described wrapping bodies.
[changing 1]
Figure G2005800375459D00021
In the formula (1), R 1, R 2, R 3Represent that respectively hydrogen atom, carbonatoms are that alkyl or the carbonatoms of 1-6 is the alkenyl of 2-4, these groups also can have substituting group.
[changing 2]
Figure G2005800375459D00022
In the formula (2), R 1, R 2, R 3, R 4Represent that respectively hydrogen atom, carbonatoms are that alkyl or the carbonatoms of 1-6 is the alkenyl of 2-4, these groups also can have substituting group.
Metal antirusting agent of the present invention is to having good inhibition effect because of getting rusty of producing of dewfall in the prolonged preservation, and the cleaning that can keep the surface of metal parts, so during the processing of the metal after preserving (plating, coating etc.), can save washing process (rust cleaning, metallic surface clean processing etc.), so save time and reduced the reagent expense.
Embodiment
As the object metal of rust-preventive agent of the present invention, mainly be iron.Rust-preventive agent of the present invention is applicable to also that the alloy with other metal such as copper, nickel, chromium, cobalt, lead, zinc, aluminium, titanium, tin, gold and silver and these metals grinds and cuts the material that cuts processing, moulding, sintering processing etc. and obtain.And, also be applicable to the product that on surfaces such as resin, glass, pottery, metallizes and obtain by methods such as bonding, crimping, plating, evaporation, ion platings.
Hydroxylamine compound by formula (1) expression specifically is preferably azanol, O-methyl hydroxylamine, O-ethyl azanol, N-methyl hydroxylamine, N, N-dimethyl hydroxylamine, N, O-dimethyl hydroxylamine, N-ethyl azanol, N, N-diethyl hydroxylamine, N, O-diethyl hydroxylamine, O, N, N-trimethylammonium azanol, N-(2-methoxy ethyl) azanol, N-allyl group azanol, N, O-diallyl azanol, O-cyclohexyl-N, N-dimethyl hydroxylamine etc.Wherein, more preferably azanol, N, N-diethyl hydroxylamine.
Hydrazine compound by formula (2) expression specifically is preferably hydrazine, methylhydrazine, ethyl hydrazine, 1,1-dimethylhydrazine, 1,2-dimethylhydrazine, 1,1-diethyl hydrazine, 1,2-diethyl hydrazine, Iproniazid, 1,2-diisopropyl hydrazine, hexamethylene hydrazine, allyl group hydrazine etc.Wherein, more preferably hydrazine, methylhydrazine, 1,1-dimethylhydrazine, 1,2-dimethylhydrazine, ethyl hydrazine, 1,1-diethyl hydrazine, 1,2-diethyl hydrazine.
In the rust-preventive agent of the present invention, the concentration of above-mentioned hydroxylamine compound or hydrazine compound is preferably 0.001-50 weight %, more preferably 0.05-30 weight %, more preferably 0.5-30 weight %.When less than 0.001 weight %, rust-proof effect is insufficient, even and above 50 weight %, can not further improve rust-proof effect, so inappropriate aspect economy.
Among the present invention, when the antirust quick-acting of needs, the composition that obtains by further interpolation alkynol in hydroxylamine compound or hydrazine compound can being remained in the absorbent resin. alkynol is fit to use 1-propine-3-alcohol, ethyl acetylene-3-alcohol, ethyl acetylene-4-alcohol, 2-butyne-1-alcohol, 3-methyl isophthalic acid-butine-3-alcohol, 3-methyl isophthalic acid-butine-4-alcohol, 1-pentyne-3-alcohol, methylpentynol, 1-hexin-3-alcohol, 3,5-dimethyl-1-hexin-3-alcohol, the 1-ethynylcyclohexanol, 1-heptyne-3-alcohol, 1-octyne-3-alcohol, 1-n-heptylacetylene-3-alcohol, 1-decine-3-alcohol, 2-butyne-1, the 4-glycol, 3-hexin-2, the 5-glycol, 3,5-dimethyl-3-hexin-2, the 5-glycol, 4-ethyl-1-octyne-carbonatomss such as 3-alcohol are the alkynol of 3-10, wherein be particularly suitable for using methylpentynol (methylparafynol), 3-methyl isophthalic acid-butine-3-alcohol (methylbutynol), 3,5-dimethyl-1-hexin-3-alcohol (dimethylated hexynol), 1-ethynylcyclohexanol etc. in the rust-preventive agent of the present invention, the concentration of alkynol is preferably 0.001-50 weight %, 0.01-10 weight % more preferably, more preferably 0.1-10 weight %. is when less than 0.001 weight %, rust-proof effect is insufficient, even and surpass 50 weight %, can not further improve rust-proof effect, so consideration such as economic aspect is inappropriate.
Absorbent resin of the present invention is to be made of polymkeric substance, and this polymkeric substance is by having crystalline texture or crosslinking structure in polymkeric substance, has when contacting with water suction and expansible ability rapidly.This polymkeric substance can be enumerated particularly, the multipolymer of multipolymer, vinyl-acetic ester and the acrylate of polyvinyl alcohol, poly-(methyl) acrylate, poly-(methyl) acrylamide, polysulfonate, polyethylene oxide, carboxymethyl cellulose, acrylate and acrylate and the hydrolyzate of starch and acrylic acid-grafted polymkeric substance etc.Above-mentioned absorbent resin is preferably the amine compound (b) that will have the wetting ability Resins, epoxy (a) of the epoxide group more than 2 in 1 molecule and have 1 grade or 2 grades amino more than 2 in 1 molecule as must composition, these compositions is reacted the cured resin that obtains.
Above-mentioned Resins, epoxy (a) is not particularly limited so long as have the hydrophilic compounds of the epoxide group more than 2 in 1 molecule at least.Above-mentioned Resins, epoxy (a) can be enumerated particularly, the polyether-type epoxy resin that obtains by ethylene glycol, glycol ether, polyoxyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol etc. and epichlorohydrin reaction, the polyvalent alcohol type Resins, epoxy that obtains by glycerine, polyglycerol, TriMethylolPropane(TMP), Sorbitol Powder etc. and epichlorohydrin reaction.In these resins, preferred polyethyleneglycol diglycidylether, polypropylene glycol diglycidyl ether, glycerol polyglycidyl ether, polyglycerol polyglycidyl ether and their mixture.The epoxy equivalent (weight) of Resins, epoxy is preferably 130-1500g/eq, more preferably 200-1000g/eq.
And above-mentioned amine compound (b) is not particularly limited so long as have the compound of 1 grade or 2 grades amino more than 2 in 1 molecule at least.Can enumerate aliphatics one-level amines such as Edamine, polyethyene diamine, polyether diamine, Diethylenetriaminee (DETA), triethylenetetramine, TEPA, benzene dimethylamine particularly; Alicyclic one-level amines such as diamino methylcyclohexane, isophorone diamine; Aromatic series such as mphenylenediamine, diaminodiphenyl-methane one-level amine; Aliphatics secondary amines such as each ethylene oxide adduct of Edamine, polyethyene diamine, polyether diamine, Diethylenetriaminee (DETA), triethylenetetramine, TEPA, benzene dimethylamine etc.; Alicyclic secondary amines such as each ethylene oxide adduct of diamino methylcyclohexane, isophorone diamine etc.; And piperazine, Dyhard RU 100 etc.Wherein preferred polyethyene diamine, polyether diamine, benzene dimethylamine, diamino methylcyclohexane, isophorone diamine.
Ratio about Resins, epoxy in the above-mentioned absorbent resin (a) and amine compound (b) is, (the epoxy equivalent (weight): Ahew) be preferably 1: 0.3 to 1: 3 of the equivalence ratio of direct-connected hydrogen atom on the nitrogen-atoms of the epoxide group of Resins, epoxy (a) and amine compound (b), more preferably 1: 0.6 to 1: 2.5, more preferably 1: 0.7 to 1: 2.2.
Above-mentioned Resins, epoxy (a) and amine compound (b) are descended processing 1-48 hour at 0-150 ℃, preferably obtain absorbent resin in 40-120 ℃ of processing curing in 2-10 hour.
At this moment, in order to adjust curing speed, also can add common known curing catalyst.For example, can enumerate tertiary amine class, imidazoles and derivative thereof etc.
With hydroxylamine compound of the present invention or hydrazine compound as the method that must composition remains in the absorbent resin, be not particularly limited, absorbent resin can be ground into suitable size, under 5-100 ℃ in the aqueous solution of hydroxylamine compound or hydrazine compound dipping kept in 0.5-72 hour.
With hydroxylamine compound of the present invention or hydrazine compound as must composition remaining in the absorbent resin and the rust-preventive agent that obtains can be used as wrapping body and uses, this wrapping body be by will be component packaged be 1000ml/m having at 25 ℃, OTR oxygen transmission rate during 60%RH 2Obtain in the wrapping material of the ventilation property that dayatm is above.Structure to air-permeable packaging material and wrapping body is not particularly limited.For example, be in the air-permeable packaging material of stacking material of base material at paper or non-woven fabrics, with tool foraminous plastics film or thin slice etc., fill maintaining, seal around will wrapping material and obtain wrapping body as the hydroxylamine compound that must composition or the absorbent resin of hydrazine compound.
The rust-preventive agent of wrapping body form is sealed in the gas-barrier container with the conservation object metal.As the spendable material of gas-barrier container bag, box, jar of gas barrier property plastics or metal etc.The said gas-blocking container specifically can be enumerated the box of being made by resins such as polyethylene, polypropylene, nylon, polyester, vinylchlorid, polystyrene, or the bag of the laminated material of making by film such as polyethylene, polypropylene, nylon, polyester or thin slice etc.
When material is plastics film or thin slice,, evaporations such as aluminium, silicon oxide, selenium oxide are used behind the surface for guaranteeing gas barrier property.In addition, also can enumerate the metal tin of making by iron, aluminium, stainless steel etc.Gas-barrier container is 50ml/m at 25 ℃, OTR oxygen transmission rate during 60%RH preferably 2Dayatm is following and be 5g/m at 40 ℃, water vapor transmission rate (WVTR) during 90%RH 2Below the day.Be 10ml/m more preferably at 25 ℃, OTR oxygen transmission rate during 60%RH 2Dayatm is following and be 1g/m at 40 ℃, water vapor transmission rate (WVTR) during 90%RH 2Below the day.
Embodiment
Specify the present invention below by embodiment and comparative example, but the present invention is not limited to following examples.
Embodiment 1
To heat in advance to 60 ℃ 82 parts polyethyleneglycol diglycidylether (デ Na コ one Le EX-841, Na ガ セ changes into (strain) system, epoxy equivalent (weight): 370g/eq) and 2 parts glycerol polyglycidyl ether (デ Na コ one Le EX-313, Na ガ セ changes into (strain) system, epoxy equivalent (weight): 141g/eq) (epoxy equivalent (weight): Ahew=1: 2.0) join in 500 milliliters the beaker, further add 0.1 part benzyldimethylamine, mix and stir as curing catalyst.To the m-xylene diamine (Ahew: 34g/eq), further stir that wherein adds 16 parts.With the shaping dies of this mixing solutions impouring aluminum, in moisture eliminator, heated 1 hour down at 80 ℃, further be warming up to 120 ℃, heated 1 hour, obtain resin cured matter.This resin cured matter is pulverized in mortar, 3 these crushed materials that restrain were flooded 24 hours down at 25 ℃ in the aqueous hydroxylamine of 100 milliliters 5 weight %.Then, the resin cured matter that contains this azanol (water-intake rate 300 weight % with suction, hydroxylamine content 5 weight %) (80 millimeters * 50 millimeters of interior dimensionss, OTR oxygen transmission rate is 1000ml/m to be filled into the air-permeable packaging material of being made by the layered product of paper/polyethylene film 2Dayatm) in, the polyethylene film face as the inboard, is sealed the edge section, make the rust-preventive agent wrapping body.This rust-preventive agent wrapping body is carried out the gasified rust-proofing test.After (according to JIS-Z-1519) test, the generation state that gets rusty of visual observation test film is 3 grades according to following standard evaluation.It the results are shown in table 1.
Zero does not cause fully and gets rusty
Less than 50% surface-area of △ test film causes and gets rusty
50% of * test film causes with top surface area and to get rusty
Embodiment 2
Except the hydrazine with 5 weight % replaces the azanol of 5 weight %, other and embodiment 1 identical carrying out.The gasified rust-proofing test-results is shown in table 1.
Embodiment 3
Except the N with 5 weight %, the N-diethyl hydroxylamine replaces outside the azanol of 5 weight %, other and embodiment 1 identical carrying out.The gasified rust-proofing test-results is shown in table 1.
Embodiment 4
Except the methylhydrazine with 5 weight % replaces the azanol of 5 weight %, other and embodiment 1 identical carrying out.The gasified rust-proofing test-results is shown in table 1.
Embodiment 5
Except the ethyl hydrazine with 5 weight % replaces the azanol of 5 weight %, other and embodiment 1 identical carrying out.The gasified rust-proofing test-results is shown in table 1.
Embodiment 6
Except with 1 of 5 weight %, the 1-dimethylhydrazine replaces outside the azanol of 5 weight %, other and embodiment 1 identical carrying out.The gasified rust-proofing test-results is shown in table 1.
Embodiment 7
Except with 1 of 5 weight %, the 2-dimethylhydrazine replaces outside the azanol of 5 weight %, other and embodiment 1 identical carrying out.The gasified rust-proofing test-results is shown in table 1.
Embodiment 8
Except polyethyleneglycol diglycidylether (デ Na コ one Le EX-861 with 91.5 parts, Na ガ セ changes into (strain) system, epoxy equivalent (weight): 551g/eq) and 8.5 parts m-xylene diamine (epoxy equivalent (weight): Ahew=1: 1.76) replace outside the m-xylene diamine of 82 parts polyethyleneglycol diglycidylether (デ Na コ one Le EX-841), 2 parts glycerol polyglycidyl ether and 16 parts other and embodiment 1 identical carrying out.The gasified rust-proofing test-results is shown in table 1.
Embodiment 9
Except polyethyleneglycol diglycidylether (デ Na コ one Le EX-861) with 86 parts, 8 parts polypropylene glycol diglycidyl ether (EX-920, Na ガ セ changes into (strain) system, epoxy equivalent (weight): 176g/eq), the isophorone diamine of 1 part benzyldimethylamine and 6 parts (Ahew: 43g/eq) (epoxy equivalent (weight): Ahew=1: 1.77) replace 82 parts polyethyleneglycol diglycidylether (デ Na コ one Le EX-841), 2 parts glycerol polyglycidyl ether, 0.1 outside benzyldimethylamine of part and 16 parts the m-xylene diamine, other and embodiment 1 identical carrying out.The gasified rust-proofing test-results is shown in table 1.
Embodiment 10
Except with 1 of 88.6 parts polyethyleneglycol diglycidylether (デ Na コ one Le EX-861), 1 part benzyldimethylamine and 11.4 parts, 3-two (amino methyl) hexanaphthene (Ahew: 36g/eq) (epoxy equivalent (weight): Ahew=1: 2.02) replace outside the m-xylene diamine of 82 parts polyethyleneglycol diglycidylether (デ Na コ one Le EX-841), 2 parts glycerol polyglycidyl ether, 0.1 part benzyldimethylamine and 16 parts other and embodiment 1 identical carrying out.The gasified rust-proofing test-results is shown in table 1.
Embodiment 11
Except with 88.3 parts polyethyleneglycol diglycidylether (デ Na コ one Le EX-861) and 11.7 parts triethylenetetramine (Ahew: 37g/eq) (epoxy equivalent (weight): Ahew=1: 2.02) replace the m-xylene diamine of 82 parts polyethyleneglycol diglycidylether (デ Na コ one Le EX-841), 2 parts glycerol polyglycidyl ether and 16 parts other and embodiment 1 identical carrying out.The gasified rust-proofing test-results is shown in table 1.
Comparative example 1
Except replace the aqueous hydroxylamine other and embodiment 1 identical carrying out with pure water.The gasified rust-proofing test-results is shown in table 1.
Comparative example 2
Except the silica gel with 5 grams replaces the absorbent resin other and embodiment 1 identical carrying out.The gasified rust-proofing test-results is shown in table 1.
Comparative example 3
Except the gac with 5 grams replaces the absorbent resin other and embodiment 1 identical carrying out.The gasified rust-proofing test-results is shown in table 1.
Embodiment 12
(デ Na コ one Le EX-861, Na ガ セ change into (strain) system, epoxy equivalent (weight): 551g/eq) join in 500 milliliters the beaker, to the ion exchanged water that wherein adds 100 parts, mix down at 60 ℃ and to stir with 88.3 parts polyethyleneglycol diglycidylethers.Triethylenetetramine (the Ahew: 37g/eq) (epoxy equivalent (weight): Ahew=1: 1.97), further stir that adds 11.7 parts therein.It was heated 2 hours in 80 ℃ moisture eliminator, obtain resin cured matter.This resin cured matter is pulverized in mortar, with these crushed materials of 5 grams under 25 ℃ at 1 of 100 milliliters 1 weight %, dipping is 5 hours in the aqueous solution of the methylparafynol of 1-diethyl hydrazine and 0.1 weight %.Utilize the resin cured matter of this dipping,, carry out the gasified rust-proofing test by making the rust-preventive agent wrapping body with embodiment 1 same procedure.It the results are shown in table 1.
Embodiment 13
Except the methylbutynol with 0.1 weight % replaces the methylparafynol of 0.1 weight %, other and embodiment 12 identical carrying out.The gasified rust-proofing test-results is shown in table 1.
Embodiment 14
With 60 parts polyethyleneglycol diglycidylethers (デ Na コ one Le EX-861, Na ガ セ changes into (strain) system, epoxy equivalent (weight): 551g/eq) join in 500 milliliters the beaker,, mix and stir to wherein adding 0.2 part benzyldimethylamine and 100 parts ion exchanged water.To the polyether diamine (Ahew: 500g/eq) (epoxy equivalent (weight): Ahew=1: 0.73), further stir that wherein adds 40 parts.It was heated 2 hours in 80 ℃ moisture eliminator, further be warming up to 90 ℃ of heating 3 hours, obtain resin cured matter.This resin cured matter is pulverized in mortar, with these crushed materials of 5 grams under 25 ℃ at 1 of 100 milliliters 1 weight %, dipping is 5 hours in the aqueous solution of the dimethylated hexynol of 2-diethyl hydrazine and 0.1 weight %.Utilize the resin cured matter of this dipping, make the rust-preventive agent wrapping body, carry out the gasified rust-proofing test with embodiment 1 same procedure.It the results are shown in table 1.
Embodiment 15
Except the 1-ethynylcyclohexanol with 0.1 weight % replaces the dimethylated hexynol of 0.1 weight %, other and embodiment 14 identical carrying out.The gasified rust-proofing test-results is shown in table 1.
Table 1
The evaluation of getting rusty
Embodiment 1 ○
Embodiment 2 ○
Embodiment 3 ○
Embodiment 4 ○
The evaluation of getting rusty
Embodiment 5 ○
Embodiment 6 ○
Embodiment 7 ○
Embodiment 8 ○
Embodiment 9 ○
Embodiment 10 ○
Embodiment 11 ○
Embodiment 12 ○
Embodiment 13 ○
Embodiment 14 ○
Embodiment 15 ○
Comparative example 1 ×
Comparative example 2 △
Comparative example 3 ×

Claims (9)

1. rust-preventive agent, it is characterized in that, this rust-preventive agent contains by the hydroxylamine compound of following formula (1) expression or the hydrazine compound of being represented by following formula (2), and absorbent resin, wherein, described hydroxylamine compound or described hydrazine compound remain on the absorbent resin, and, the concentration of described hydroxylamine compound or the concentration of described hydrazine compound are 0.001-50 weight %, described absorbent resin reacts the cured resin that obtains for the amine compound (b) that will have the wetting ability Resins, epoxy (a) of the epoxide group more than 2 and have 1 grade or 2 grades amino more than 2 in 1 molecule in 1 molecule
Figure F2005800375459C00011
In the formula (1), R 1, R 2, R 3Represent that respectively hydrogen atom, carbonatoms are that alkyl or the carbonatoms of 1-6 is the alkenyl of 2-4, these groups also can have substituting group,
Figure F2005800375459C00012
In the formula (2), R 1, R 2, R 3, R 4Represent that respectively hydrogen atom, carbonatoms are that alkyl or the carbonatoms of 1-6 is the alkenyl of 2-4, these groups also can have substituting group.
2. rust-preventive agent according to claim 1, wherein, described Resins, epoxy (a) is for being selected from least a in the group of being made up of polyethyleneglycol diglycidylether, polypropylene glycol diglycidyl ether, glycerol polyglycidyl ether and polyglycerol polyglycidyl ether.
3. rust-preventive agent according to claim 1, wherein, described amine compound (b) is for being selected from least a in the group of being made up of polyethyene diamine, polyether diamine, benzene dimethylamine, two (amino methyl) hexanaphthene and isophorone diamine.
4. rust-preventive agent according to claim 1, wherein, the compound of being represented by formula (1) is azanol or N, the N-diethyl hydroxylamine.
5. rust-preventive agent according to claim 1, wherein, by the compound of formula (2) expression for being selected from hydrazine, methylhydrazine, ethyl hydrazine, 1,1-dimethylhydrazine, 1,2-dimethylhydrazine, 1,1-diethyl hydrazine and 1, at least a in the 2-diethyl hydrazine.
6. rust-preventive agent according to claim 1, wherein, described rust-preventive agent also contains the alkynol that carbonatoms is 3-10.
7. rust-preventive agent according to claim 6, wherein, described alkynol is for being selected from methylpentynol, 3-methyl isophthalic acid-butine-3-alcohol, 3, at least a in the pure and mild 1-ethynylcyclohexanol of 5-dimethyl-1-hexin-3-.
8. wrapping body, this wrapping body is packed any described rust-preventive agent in the claim 1 to 7 and is obtained with poromeric material.
9. a rust-proofing method is characterized in that, this method comprises metal parts is kept in the gas-barrier container with the described wrapping body of claim 8.
CN2005800375459A 2004-11-17 2005-11-15 Antirust agent Expired - Fee Related CN101052747B (en)

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