CN102388166B - Zinc-based black rust inhibitor, rust inhibiting coating film, and rust inhibiting metal member - Google Patents
Zinc-based black rust inhibitor, rust inhibiting coating film, and rust inhibiting metal member Download PDFInfo
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- CN102388166B CN102388166B CN201080016454.8A CN201080016454A CN102388166B CN 102388166 B CN102388166 B CN 102388166B CN 201080016454 A CN201080016454 A CN 201080016454A CN 102388166 B CN102388166 B CN 102388166B
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- 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
- C09D5/10—Anti-corrosive paints containing metal dust
- C09D5/106—Anti-corrosive paints containing metal dust containing Zn
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- 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
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
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- Paints Or Removers (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
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Abstract
Disclosed are: a rust inhibiting coating film which exhibits excellent rust inhibiting properties as a black rust inhibitor, while having a sufficient black color tone; a rust inhibiting metal member; and a zinc-based black rust inhibitor which is capable of forming the rust inhibiting coating film. Specifically disclosed is a zinc-based black rust inhibitor which is characterized by containing (1) a zinc pigment and/or a zinc alloy pigment, (2) black synthetic iron oxide and (3) a phosphoric acid-based rust inhibiting pigment in such amounts that the mass ratio of (1) the zinc pigment and/or zinc alloy pigment to (2) the black synthetic iron oxide ((1)/(2)) is within the range from 85/15 to 65/35 and the mass ratio of (2) the black synthetic iron oxide to (3) the phosphoric acid-based rust inhibiting pigment ((2)/(3)) is within the range from 70/30 to 50/50. Also specifically disclosed are a rust inhibiting coating film which is formed from the zinc-based black rust inhibitor, and a rust inhibiting metal member in which the rust inhibiting coating film is provided on the surface of a metal base.
Description
Technical field
The present invention relates to a kind of zinc is black anti-rust agent, antirust epithelium and anticorrosive metal part, specifically relate to and a kind ofly have as the good rustless property of black anti-rust agent and there is antirust epithelium and the anticorrosive metal part of sufficient black tone, and the zinc that can form described antirust epithelium is black anti-rust agent.
Background technology
In metal anti-corrosion paint, we know such as zinc rich paint (zinc rich paint) etc., because the metal-powder that contains zinc pigment and aluminium powder form etc. is as rust-stabilising pigment, because ionization tendency is larger than iron etc., can bring into play sacrifice preservative effect.Zinc rich paint is divided into and has used the zinc rich paint of organic solvent and zinc rich paint that can dilute with water.In zinc rich paint with an organic solvent, have the organic zinc rich paint using the organic system resin of epoxy resin etc. as tackiness agent, and to use tetraethyl silicate etc. inorganic be the inorganic zinc rich paint etc. of tackiness agent.In addition, the zinc rich paint of water system has silicate that to using water glass etc. be representative as the zinc rich paint of tackiness agent, and the zinc rich paint using chromic acid as tackiness agent.
Particularly contain the zinc rich paint of chromic acid, the chromic acid composition being comprised in liquid is given the self-regeneration function of filming, sacrifice preservative effect by anti-rust coating significantly improves rustless property, simultaneously, as the zinc adding and the surperficial inhibitor (inhibitor) that forms stable synthetic film of aluminum particulate, prevent that binder aqueous solution from producing reacting of hydrogen with metal-powder in coating.Very good in the erosion resistance of film containing the rust proof paint of chromic acid composition like this, thereby be widely used in the bolt, nut etc. of automobile.
But, from environmental issue, consider, in recent years for the demand containing the chromium-free metal rust proof paint of chromic acid composition is more and more not higher, thereby also there is the scheme of a lot of chromium-free metal rust proof paints.
For example, in patent documentation 1, recorded " a kind of anticolodal being formed by water-soluble synthetic resin tackiness agent, the metal fine powder oxidation inhibitor last and this metal larger than the ionization tendency of metal to be treated " (claim 1).
In addition, in patent documentation 2, recorded " the self-sacrifice shaped metal sanitas that a kind of larger metal-powder, water-insoluble thermoplastic resin powder, water soluble anti-rust agent, interfacial agent, tackifier and water of ionization tendency of the ratio metal to be treated by one or more forms " (claim 1).
In patent documentation 3, recorded " at the bottom of a kind of iron-based with coating; be carry out after degreasing and sandblasting, applying at the bottom of iron-based containing zinc end epoxypaint; should be containing zinc end epoxypaint; be the vehicle (vehicle) that epoxy resin is main component of take for 10 weight parts, the composition that contains zinc end 20～200 weight parts, thermal expansivity powder 0.05～0.5 weight part " (claim 1).
In addition, claim 4 has been recorded and " a kind ofly not containing the water dilution type coating composition of chromium, has been applied on base material and makes its heat embrittlement, giving base material corrosion protection, it is characterized in that, containing: (A) high boiling point organic liquid; (B) granulated metal; (C) tackifier; And, (D) silane adhesive of approximately 3～20 % by weight of formation composition in its entirety weight " (claim 1).
The anticolodals of recording as patent documentation 1～4 etc., containing the rust-preventive agent of a large amount of zinc, are all generally after coating, to show silver color.
But, recently due to the metal parts that etc. high-temperature part is processed of the engine at automobile etc., need it to present black around.If around the engine of automobile, the parts of below are black, re-use and applied bolt that zinc is rust-preventive agent, nut etc., silver color can be obvious especially, causes outward appearance not ideal enough.Therefore, be to be on rust-preventive agent, to apply blackwash as cover warnish at zinc now, still, if at this moment use outer layer coating, can increase processing engineering, make operation become complicated.In addition, if the silver color of the impaired ，Qi of the outer layer coating using lower floor also can be exposed, cause outward appearance undesirable.
In addition, in order to improve the above-mentioned problem points that presents silver color, for example also occurred, by the method for the rust-preventive agent black that contains a large amount of zinc, the method for mixing carbon.
Use carbon as the technology of black developing agent, for example in patent documentation 5, recorded " a kind of black zinc end coating composition; by (A) resiniferous forming component of filming of 100 weight parts, and (B) zinc of 50～86 weight parts corresponding thereto (C) electroconductibility carbon last, 1～10 weight part combines " (claim 1).But " the black zinc end coating compositions " recorded as patent documentation 5 etc. if added a large amount of carbons, can form local element because of carbon in epithelium, thus the problem that causes rust-preventing characteristic to decline.
In addition, if common black iron oxide is added into containing zinc sanitas, because black iron oxide is poor for the hidden rate of the silver color based on zinc, when the film with 5～10 μ m thickness being formed on to bolt etc., not only cannot obtain sufficient blackness, also can produce variable color because of the rigor condition such as high temperature of installation position, occur red change etc., cannot the desirable black of long term maintenance.
Look-ahead technique document
Patent documentation
Patent documentation 1: flat No. 06-41472 of Japanese Unexamined Patent Publication
Patent documentation 2: No. 2001-303279, Japanese Unexamined Patent Publication
Patent documentation 3: flat No. 10-68085 of Japanese Unexamined Patent Publication
Patent documentation 4: flat No. 10-46058 of Japanese Unexamined Patent Publication
Patent documentation 5: flat No. 06-49393 of Japanese Unexamined Patent Publication
Summary of the invention
The problem that invention will solve
The present invention carries out based on above-mentioned background, the object of the invention is to, and overcomes that on the metal base of iron and steel etc., to carry out zinc be that rust-preventive agent is processed, in metallic substrate surface, formed after overlay film in the past, and its surface is the problem of silver color.
That is, the object of the invention is to, provide a kind of and have as the good rustless property of black anti-rust agent and there is antirust epithelium and the anticorrosive metal part of sufficient black tone, and the zinc that can form described antirust epithelium is black anti-rust agent.
Solve the means of problem
The present inventor in view of the above problems, the zinc in order to develop with good characteristic is black anti-rust agent, carried out various research, the zinc that final discovery contains specific constituent with specific mass ratio is black anti-rust agent and antirust overlay film, this zinc is black anti-rust agent and antirust overlay film, particularly using this zinc is the antirust overlay film that black anti-rust agent forms in metallic substrate surface, has good rust-preventing characteristic and black, can reach above-mentioned purpose.Therefore, the present inventor has completed the present invention based on this understanding.
As the means that solve above-mentioned problem,
Claim 1 provides a kind of black anti-rust agent, it is characterized in that, contains: (1) zinc pigment and/or zinc alloy pigment; (2) black synthetic iron oxide; (3) phosphoric acid is rust-stabilising pigment, wherein, the mass ratio of described (1) zinc pigment and/or zinc alloy pigment and described (2) black synthetic iron oxide ((1)/(2)) is 85/15～65/35, described (2) black synthetic iron oxide and described (3) phosphoric acid are that the mass ratio ((2)/(3)) of rust-stabilising pigment is 70/30～50/50, and, do not contain carbon
It is black anti-rust agent that claim 2 further defines zinc claimed in claim 1, it is characterized in that, contains: (4) silane coupling agent and/or titanium couplant; (5) alcohol series solvent,
Claim 3 provides a kind of antirust epithelium, it is characterized in that, contains: (1) zinc pigment and/or zinc alloy pigment; (2) black synthetic iron oxide; (3) phosphoric acid is rust-stabilising pigment, wherein, the mass ratio of described (1) zinc pigment and/or zinc alloy pigment and described (2) black synthetic iron oxide ((1)/(2)) is 85/15～65/35, described (2) black synthetic iron oxide and described (3) phosphoric acid are that the mass ratio ((2)/(3)) of rust-stabilising pigment is 70/30～50/50, and, do not contain carbon
Claim 4 further defines antirust epithelium claimed in claim 3, it is characterized in that: contain (4) silicon oxide and/or titanium oxide,
Claim 5 further defines claim 3 or antirust epithelium claimed in claim 4, it is characterized in that: be to be that black anti-rust agent is dry at 70～120 ℃ by claim 1 or zinc claimed in claim 2, and burn-back form at 250～360 ℃,
Claim 6 provides a kind of anticorrosive metal part, it is characterized in that: on the surface of metal base, there is the antirust epithelium described in any one of claim 3～5,
Claim 7 further defines anticorrosive metal part claimed in claim 6, it is characterized in that: described antirust epithelium has the thickness of 5～20 μ m.
Invention effect
Antirust overlay film of the present invention, owing to containing above-mentioned specific constituent, in addition with specific mass ratio, because the surface of anticorrosive metal part of the present invention has antirust overlay film of the present invention, therefore,, when can bringing into play good rust-preventing characteristic, can also present the black of excellent color tone.Zinc of the present invention is black anti-rust agent, owing to containing above-mentioned specific constituent with specific mass ratio, when being used as antirust overlay film, when can bringing into play good rust-preventing characteristic, can also present the black of excellent color tone.Therefore, can cross the present invention, can provide a kind of and have as the good rustless property of 2 black anti-rust agent and there is antirust epithelium and the anticorrosive metal part of sufficient black tone, and the zinc that can form described antirust epithelium is black anti-rust agent.
embodiment
Zinc of the present invention is black anti-rust agent, with mass ratio described later, contains (1) zinc pigment and/or zinc alloy pigment; (2) black synthetic iron oxide; (3) phosphoric acid is rust-stabilising pigment.That is, the zinc of these 2 inventions is black anti-rust agent, can be called with mass ratio described later and contain (1) zinc pigment and/or zinc alloy pigment; (2) black synthetic iron oxide; (3) phosphoric acid is the composition of rust-stabilising pigment.
Described (1) zinc pigment and/or zinc alloy pigment, can be that crushed material, the solution of zinc and/or zinc alloy minces, particle shape thing etc., for example, and the platy particle of the powder of zinc and/or zinc alloy, zinc and/or zinc alloy etc.Forming the metal beyond the zinc of described zinc alloy, can be such as aluminium, tin, magnesium, nickel, cobalt, manganese etc.As zinc alloy, alloy of the alloy of the zinc alloy of zinc and aluminium, zinc and tin, zinc and aluminium and tin etc. preferably.From the rustless property of the antirust overlay film that is formed, consider, in described zinc alloy, the containing ratio of zinc is preferably greater than 50 quality %.For example, in the zinc alloy of described zinc and aluminium, more than the containing ratio of zinc is preferably 80 quality %, more preferably state is more than 85 quality %.In the zinc alloy of described zinc and tin, more than the containing ratio of zinc is preferably in 70 quality %, more preferably state is more than 80 quality %.
For shape of zinc pigment and zinc alloy pigment etc., there is no particular limitation, but platy particle preferably.That is, as zinc pigment and/or zinc alloy pigment, can be, the thin slice etc. of zinc alloy of thin slice, zinc and the tin of the zinc alloy of zinc thin slice, zinc and aluminium.When platy particle is used, in total quality, preferably have at least the platy particle of 50 quality % to there is the major diameter of not enough approximately 25 μ m zinc pigment and/or zinc alloy pigment, have at least the platy particle of 90 quality % to there is the major diameter of not enough approximately 20 μ m.The thickness of described thin slice can be 0.05～1 μ m left and right, preferably 0.1～0.5 μ m left and right.The major diameter of thin slice can be measured by laser diffraction/formula particle footpath measure of spread device at random, and its thickness can be measured by the electron microscope of section.
Zinc pigment and/or zinc alloy pigment, such as being that the solvent that contains in black anti-rust agent etc. forms after pulpous state by zinc, there will not be powder to disperse, and at zinc, is that dispersiveness in black anti-rust agent is more high, thereby comparatively desirable.
Zinc pigment and/or zinc alloy pigment are preferably high purity, are in fact preferably purity more than 99 quality %.
Described (2) black synthetic iron oxide, can be the thermotolerance synthetic iron oxide that is black, for example, can be with (FeO) x-(Fe
2o
3) (x is the molefraction of (FeO) to y, and y is (Fe
2o
3) molefraction, x+y is 1.) Z 250 or its hydrate that represent.Described Z 250 is also recited as Fe
3o
4, in the cubic crystal of inverse spinel dot matrix, at the apex configuration oxygen of cubic lattice, 1/2nd configuration Fe on 8 body summits centered by oxygen
2+ion, 1/2nd and 4 body apex configuration Fe on remaining 8 body summits
3+ion.FeO and γ-Fe
2o
3the configuration of oxygen all get identical cubic lattice.By oxidizing reaction or reduction reaction, these 3 kinds of compounds are easy to mutual conversion, but final structural difference is at this moment very little.According to different test portions, Fe
3o
4it may be also indefinite scale compound.For shape of described black synthetic iron oxide etc., be not particularly limited, such as being spherical, octahedra shape, Powdered, sheet etc., its median size etc. be also not particularly limited.
As black synthetic iron oxide, for example, trade(brand)name " ETB-300 (TAROX synthetic iron oxide) " (manufacture of titanium Industrial Co., Ltd), trade(brand)name " BL-100, BL-500 etc. " (manufacture of titanium Industrial Co., Ltd) etc., can be easy to obtain.
Described (3) phosphoric acid is rust-stabilising pigment, such as being zinc phosphate, alkaline phosphatase zinc, polyphosphoric acid zinc, positive polyphosphoric acid zinc, calcium phosphate zinc, trimagnesium phosphate zinc, trimagnesium phosphate, zinc phosphite, phospho-molybdic acid zinc, aluminium triphosphate, aluminum phosphite, phosphorous acid calcium etc.Wherein, from the viewpoint of easy acquired grade, consider, preferably zinc phosphate, polyphosphoric acid zinc, aluminum phosphate etc.
As phosphoric acid, being rust-stabilising pigment, can be such as trade(brand)name " rust-stabilising pigment K-White#82, #84, #84S, #85, #94, #105 " (manufacture of TAYCA Co., Ltd.), trade(brand)name " rust-stabilising pigment ZP-DL, P-WF, P-W-2, D-1, ZP-50S, ZP-SB, ZP-HS, MZP-500, MP-620PMG, ZP-600 " (manufacture of KIKUCHI COLOR Co., Ltd.), trade(brand)name " EXPERT NP-530, NP-1530, NP-1020, NP-1102 " (manufacture of Dong Bang pigment Co., Ltd.) etc.
Zinc of the present invention is black anti-rust agent, except described (1) zinc pigment and/or zinc alloy pigment, described (2) black synthetic iron oxide and described (3) phosphoric acid are rust-stabilising pigment, can also contain as required other compositions such as (4) silane coupling agent and/or titanium couplant, (5) alcohol series solvent.
Described (4) silane coupling agent and/or titanium couplant can be for example the couplants shown in following general formula (1):
General formula (1): (R
1)
m-Met-(OR
2)
4-m
(here, the Met in general formula (1) represents Si atom or Ti atom, R
1and R
2represent respectively to have the side chain of identical or different substituent carbon number 1～8 or the hydrocarbon base of straight chain, m represents 0～3 integer.)
Described silane coupling agent can be following general formula (2): (R
1)
m-Si-(OR
2)
4-m(the R in general formula (2) here,
1and R
2and the R in m and above-mentioned general formula (1)
1and R
2and m is identical.) shown in couplant, can be specifically tetramethoxy-silicane (tetramethoxysilane), tetraethoxysilane (tetraethoxysilane), four positive propoxy silane (tetra-n-propoxysilane), tetraisopropoxysilan (tetraisopropoxysilane), four n-butoxy silane (tetra-n-butoxysilane), tetraisobutoxy-silicane alkane (tetra-iso-butoxysilane), four butoxy silanes (tetra-sec-butoxysilane), four-uncle-butoxy silane (tetra-t-butoxysilane), triethoxy amyl group silane (triethoxypenthylsilane), methyltrimethoxy silane (trimethoxymethylsilane), trimethoxy (methyl) silane (trimethoxy (methyl) silane), ethyl triethoxysilane (triethoxyethylsilane), trimethoxy (propyl group) silane (trimethoxy (propyl) silane), monosubstituted ethoxy Trimethoxy silane (monoethoxytrimethoxysilane), single butoxy Trimethoxy silane (monobutoxytrimethoxysilane), single pentyloxy Trimethoxy silane (monopentoxytrimethoxysilane), mono methoxy Trimethoxy silane (monohethoxytrimethoxysilane), dimethoxy diethoxy silane (dimethoxydiethoxysilane), dimethoxy dibutoxy silane (dimethoxydibutoxysilane), ethyl trimethoxy silane (ethyltrimethoxysilane), ethyl triethoxysilane (ethyltriethoxysilane), dimethyldimethoxysil,ne (dimethyldimethoxysilane), diethyl dimethoxy silane (diethyldimethoxysilane), γ-Racemic glycidol propoxy-Trimethoxy silane (glycidoxypropyltrimethoxysilane), γ-Racemic glycidol propoxy-triethoxyl silane (glycidoxypropyltriethoxysilane), γ-Racemic glycidol propoxy-methyl dimethoxysilane (glycidoxypropylmethyldimethoxysilane) etc.
Described silane coupling agent, what be wherein more suitable for has tetramethoxy-silicane, tetraethoxysilane, four butoxy silanes, γ-Racemic glycidol propoxy-methyl dimethoxysilane and a γ-Racemic glycidol Trimethoxy silane (glycidoxytrimethoxysilane) etc.
In the present invention, described silane coupling agent, except the described monomer shown in above-mentioned general formula (2), can also be used the heavy polymer obtaining after one kind or two or more described monomer reaggregation.
Described titanium couplant can be following general formula (3): (R
1)
m-Ti-(OR
2)
4-m(the R in general formula (3) here,
1and R
2and the R in m and above-mentioned general formula (1)
1and R
2and m is identical.) shown in couplant, can be specifically, tetramethoxy titanium (tetramethoxytitanium), four titanium propanolates (tetrapropoxytitanium), tetraisopropoxy titanium (tetra-iso-propoxytitanium), four titanium butoxide (tetrabutoxytitanium), four (2-ethylhexyl oxygen) titanium (tetrakis (2-ethylhexyloxy) titanium), titanium-isopropoxy octenol hydrochlorate (titanium-iso-propoxy octylene glycollate), two (propanedioxytitaniumbis) (etheric acid ethyl esters) (ethyl acetoacetate) of the third dioxy base titanium etc.
Described titanium couplant, what be wherein more suitable for has tetramethoxy titanium, four titanium propanolates, tetraisopropoxy titanium, four titanium butoxide etc.
In the present invention, described titanium couplant, except the described monomer shown in above-mentioned general formula (3), can be used the heavy polymer obtaining after one kind or two or more described monomer reaggregation.
Described (5) alcohol series solvent, the organic solvent preferably mixing arbitrarily with water, has the unit price of hydrocarbon base or the alcohols of multivalence of the straight or branched of carbon number 1～8.Such alcohols is unit price or multivalence alcohols, the ethers of multivalence alcohol and the ester class of multivalence alcohol of carbon number 2～4 preferably.
Described alcohol series solvent, is preferably used at least a kind of solvent selecting in the group who forms from the ester class of the ethers by 1 valency alcohol, multivalence alcohol, multivalence alcohol, multivalence alcohol.As described monovalent alcohol, such as being methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol, n-butyl alcohol, 2-butanols, isopropylcarbinol, tert-butanols etc.As described multivalence alcohol, such as being ethylene glycol, glycerol, dipropylene glycol, glycol ether, contracting two glycerol (diglycerine), two contracting dipropylene glycols, triglycol, tripropylene glycol (tripropylene glycol), butyleneglycol (butylene glycol) etc.Ethers as described multivalence alcohol, it can be for example the monoalkyl ethers of described multivalence alcohol, as described monoalkyl ethers, can be specifically ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diglycol monotertiary propyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, DPE, dipropylene glycol list propyl ether, Dipropylene glycol mono-n-butyl Ether etc.The ester class of described multivalence alcohol, such as being single short-chain aliphatic ester class of described multivalence alcohol etc., as single short-chain aliphatic ester class of described multivalence alcohol, can be specifically ethylene glycol acetate, Diethylene Glycol monoacetate, propylene glycol monoacetate, dipropylene glycol monoacetate etc.
Described other composition can be the various additives that are conventionally added in coating.As described various additives, such as being interfacial agent, tackifier, defoamer, dispersion agent, tinting material, pigment extender, lubricant etc.Described interfacial agent, as long as the composition mixing can disperse, can be ionic promoting agent, nonionic promoting agent etc.Described tackifier, such as being hydroxy ethyl cellulose, methylcellulose gum, Vltra tears, hydroxyethyl ethylcellulose, MEC, xanthan gum etc.Zinc of the present invention is to contain tackifier in black anti-rust agent, and can make zinc is that black anti-rust agent keeps suitable viscosity, thereby keeps suitable coating amount when coating.In addition, zinc of the present invention is the chromium not containing in black anti-rust agent such as sexavalent chrome etc.
At zinc of the present invention, be in black anti-rust agent, also can contain alcohol system solvent in addition, if zinc is to contain described solvent in black anti-rust agent, can improve its transaction capabilities etc.As described solvent, can be organic solvent except described (5) alcohol series solvent, water etc., but the pollution equal angles of atmosphere be considered when dry, described solvent is water preferably.For described water, be not particularly limited, such as being the less water of foreign matter content such as Purified Water, deionized water.
Zinc of the present invention is that black anti-rust agent contains described (1) zinc pigment with specific mass ratio and/or zinc alloy pigment, described (2) black synthetic iron oxide and described (3) phosphoric acid are rust-stabilising pigment.; the mass ratio of described (1) zinc pigment and/or zinc alloy pigment and described (2) black synthetic iron oxide ((1)/(2)) is 85/15～65/35, and described (2) black synthetic iron oxide and described (3) phosphoric acid are that the mass ratio ((2)/(3)) of rust-stabilising pigment is 70/30～50/50.
Be 85/15 to compare with described (1) zinc pigment and/or zinc alloy pigment and the mass ratio ((1)/(2)) of described (2) black synthetic iron oxide, if it is large that the mass ratio of described (1) zinc pigment and/or zinc alloy pigment becomes, the mass ratio of described (2) black synthetic iron oxide diminishes relatively, may cause the tone of the antirust overlay film of acquisition to be light black.In addition, be 65/35 to compare with described mass ratio ((1)/(2)), if the mass ratio of described (1) zinc pigment and/or zinc alloy pigment diminishes, may cause the rustless property of the antirust overlay film that obtains to reduce.
Therefore,, for the tone of the antirust overlay film that makes to obtain is better black, can brings into play better rustless property simultaneously, described mass ratio ((1)/(2)) is preferably 85/15～75/25.
The mass ratio ((2)/(3)) that is rust-stabilising pigment with described (2) black synthetic iron oxide and described (3) phosphoric acid is 70/30 to compare, if it is large that the quality of described (2) black synthetic iron oxide becomes, may cause the rustless property of the antirust overlay film of acquisition to decline.In addition, be 50/50 to compare with described mass ratio ((2)/(3)), if the quality of described (2) black synthetic iron oxide diminishes, may cause the tone of the antirust overlay film that obtains to be light black.
Therefore,, for the tone of the antirust overlay film that makes to obtain is better black, can brings into play better rustless property simultaneously, described mass ratio ((2)/(3)) is preferably 70/30～60/40.
Like this, at zinc of the present invention, be in black anti-rust agent, if described mass ratio ((1)/(2)) and described mass ratio ((2)/(3)) all, in described scope, can be brought into play better rustless property so that the tone of the antirust overlay film obtaining is better black, the while.
At zinc of the present invention, be in black anti-rust agent, when needs contain described (4) silane coupling agent, when the total quality that is black anti-rust agent at described zinc is 100 quality %, the containing ratio of described silane coupling agent can be 1～30 quality %, more preferably 2～20 quality %, it would be desirable 3～15 quality %.If the containing ratio of silane coupling agent is in above-mentioned scope, the antirust overlay film of acquisition can bring into play higher epithelium physical property and erosion resistance.
In addition, at zinc of the present invention, be in black anti-rust agent, when needs contain described (4) titanium couplant, when the total quality that is black anti-rust agent at described zinc is 100 quality %, the containing ratio of described titanium couplant can be 1～30 quality %, more preferably 2～20 quality %, it would be desirable 3～15 quality %.If the containing ratio of titanium couplant is in above-mentioned scope, the antirust overlay film of acquisition can bring into play higher epithelium physical property and erosion resistance.
At zinc of the present invention, be in black anti-rust agent, when needs contain described silane coupling agent and described titanium couplant, containing ratio is separately in above-mentioned scope, the total containing ratio of described silane coupling agent and described titanium couplant, can be 1～30 quality %, more preferably 2～20 quality %, it would be desirable 3～15 quality %.
At zinc of the present invention, be in black anti-rust agent, when needs contain described (5) alcohol series solvent, when the total quality that is black anti-rust agent at described zinc is 100 quality %, the containing ratio of described alcohol series solvent is preferably 0.1～20 quality % left and right.As long as the containing ratio of alcohol series solvent is in above-mentioned scope, by zinc of the present invention being that black anti-rust agent applies, be dried, in the process of burn-back, the antirust epithelium of formation, can show the unusual effect of the epithelium of formation homogeneous.
At zinc of the present invention, be in black anti-rust agent, when needs contain described other composition, should suitably adjust its containing ratio according to heterogeneity, make it to reach the degree of conventionally adding in coating.For example, at zinc of the present invention, be in black anti-rust agent, when needs contain described interfacial agent, when the total quality that is black anti-rust agent at described zinc is 100 quality %, the containing ratio of described interfacial agent is preferably 0.1～10 quality % left and right.In addition, at zinc of the present invention, be in black anti-rust agent, when needs contain described tackifier, when the total quality that is black anti-rust agent at described zinc is 100 quality %, the containing ratio of described tackifier is preferably 0.1～2.0 quality % left and right.As long as the containing ratio of described tackifier is in described scope, just can suitably keep zinc is the viscosity of black anti-rust agent, thereby keeps suitable coating amount when coating.
At zinc of the present invention, be in black anti-rust agent, when needs contain described solvent, from the viewpoint of zinc, be storage stability, handlability of black anti-rust agent etc., it for zinc, is the total quality of black anti-rust agent, should suitably adjust the amount of described solvent, described in making, (1) zinc pigment and/or zinc alloy pigment, described (2) black synthetic iron oxide and described (3) phosphoric acid are that the total quality of rust-stabilising pigment is 20～50 quality %.
Zinc of the present invention is black anti-rust agent, can be used as common coating and carries out same manufacture.For example, can, according to described specific mass ratio, each above-mentioned composition be mixed to manufacture by mixing machine.Zinc of the present invention is black anti-rust agent, when containing described (5) alcohol series solvent and/or described solvent, can, according to described specific mass ratio, each composition be disperseed to manufacture in these solvents.In addition, for the composition of more difficult dispersion in described (5) alcohol series solvent or described solvent, can in advance high density solvent be disperseed in a small amount of dispersion medium, carry out again subsequently final mixing and manufacture.
Zinc of the present invention is black anti-rust agent, for example, after the coating of the surface of metal base, by dry and burn-back, forms antirust overlay film.That is, antirust overlay film of the present invention, by being that black anti-rust agent is dried, burn-back obtains by zinc of the present invention.
Described metal base, such as being metal formed article of iron, steel etc. etc.As long as these metal formed articles have, can apply the surface that zinc of the present invention is black anti-rust agent, to its shape, there is no particular limitation.Described metal formed article can be such as automobile metal molding, metal formed article etc. for civil construction.As automobile metal molding, it can be specifically web member of various tabular molding, screw, bolt, nut, packing ring etc. etc., as civil construction metal formed article, it can be specifically the web member etc. of the screw that uses such as various tabular molding, electric car, bolt, nut, packing ring etc.
Described metal parts, before coating zinc of the present invention is black anti-rust agent, as pre-treatment, can suitably implement based on solvent carry out the degreasing engineering of degreasing, in order to improve that adhibit quality carries out the Surface Treatment Engineering of alligatoring by shot-peening material and for except the sandblast engineering of descaling etc.Described degreasing engineering, Surface Treatment Engineering and sandblast engineering etc., can adopt the condition of common enforcement and method to carry out.
When forming antirust overlay film of the present invention, be on the surface of described metal base of having implemented according to demand above-mentioned pre-treatment, applying zinc of the present invention is black anti-rust agent.Described zinc is the coating engineering of black anti-rust agent, such as passing through impregnation method, rotation mode, spray pattern etc., conventionally implements 1～3 time.Described zinc is that black anti-rust agent is applied like this, making its thickness after burn-back is for example 5～20 μ m, in other words, although the amount that will be the additive in black anti-rust agent according to described zinc determines, the solid-state part that should to make based on (1) zinc pigment and/or zinc alloy pigment, (2) black synthetic iron oxide, (3) phosphoric acid be rust-stabilising pigment etc. is 5～35g/m
2(50～350mg/dm
2) left and right adhesion amount apply.
When forming antirust overlay film of the present invention, next, at 70～120 ℃, to the described zinc having applied, be that for example 10～20 minutes be dried carried out in black anti-rust agent.By described zinc be black anti-rust agent dry after, can remove described zinc according to demand is described (5) the alcohol series solvent that contains in black anti-rust agent and/or described solvent etc., forms coating overlay film.Described zinc is the dry engineering of black anti-rust agent, can use the enforcements such as normally used well heater, drying machine.
When forming antirust overlay film of the present invention, next, by dry coating overlay film at 250～360 ℃, be preferably in and at 300～355 ℃, carry out burn-back.The burn-back engineering of coating overlay film can embodiment as time of 20 minutes～2 hours, preferably 30 minutes～40 minutes.By after the burn-back of described coating overlay film, can form antirust overlay film of the present invention like this.
Like this, just can on the surface of described metal base, form antirust overlay film of the present invention.In the present invention, can by described coating engineering, dry engineering and the combination of burn-back engineering, repeatedly implement according to demand, for example 2 times or 3 times, the antirust overlay film of formation multilayered structure.
The of the present invention antirust overlay film forming like this, contain (1) zinc pigment and/or zinc alloy pigment, (2) black synthetic iron oxide, (3) phosphoric acid is rust-stabilising pigment, wherein, the mass ratio of described (1) zinc pigment and/or zinc alloy pigment and described (2) black synthetic iron oxide ((1)/(2)) is 85/15～65/35, and described (2) black synthetic iron oxide and described (3) phosphoric acid are that the mass ratio ((2)/(3)) of rust-stabilising pigment is 70/30～50/50.In antirust overlay film of the present invention, described (1) zinc pigment and/or zinc alloy pigment, described (2) black synthetic iron oxide and described (3) phosphoric acid are rust-stabilising pigment, with zinc of the present invention be that black anti-rust agent is basic identical.In addition, the ideal range of described mass ratio ((1)/(2)) and described mass ratio ((2)/(3)) is also that black anti-rust agent is basic identical with zinc of the present invention.Therefore, antirust overlay film of the present invention has the good rustless property as black anti-rust agent, and has sufficient black tone.
Antirust overlay film of the present invention, specifically, in " salt spray testing " recorded in JIS K 5600-7-1:1999, its rustless property is, till producing red rust, to need more than 750 hours, more preferably more than 1000 hours.In addition, antirust overlay film of the present invention, specifically, in " black tone " recorded, has the L value lower than 50 in JIS K 5600-4-6:1999.
In antirust overlay film of the present invention, containing from zinc of the present invention is the silicon oxide of described (4) silane coupling agent that contains of black anti-rust agent and/or titanium couplant and/or titanium oxide and described other additive.
In antirust overlay film of the present invention, when the total quality of described antirust overlay film is 100 quality %, the containing ratio of described silicon oxide and/or titanium oxide, can be 1～30 quality %, and more preferably 2～20 quality %, it would be desirable 3～15 quality %.If the containing ratio of described silicon oxide and/or titanium oxide is in above-mentioned scope, the antirust overlay film of acquisition can bring into play higher epithelium physical property and erosion resistance.In addition, the total containing ratio of described silicon oxide and titanium oxide, can be 1～30 quality %, and more preferably 2～20 quality %, it would be desirable 3～15 quality %.
The antirust overlay film forming in a manner described, as mentioned above, can be according to suitable its thickness of adjusting such as the purposes of the kind of metal base, metal base, but as described later, owing to bringing into play higher rustless property when thering is the black that tone is good, therefore can be formed film.For example, antirust overlay film of the present invention can also be adjusted to the thickness of 5～20 μ m, more preferably the thickness of 5～15 μ m.Therefore, by the present invention, even if described metal base is 2 above components bonding or the parts of locking, such as described web member etc., also can be in the situation that do not destroy required connection state, for web member is given rustless property and the good black of tone.
Anticorrosive metal part of the present invention, is on the surface of described metal base, and having zinc of the present invention is the black anti-rust agent described antirust overlay film that burn-back forms in a manner described.Therefore, by zinc of the present invention, be black anti-rust agent, even if do not form black, be that lower coating and/or black are fastened coating, also can give higher rustless property and the good black of tone for described metal base.So anticorrosive metal part of the present invention has as the good rustless property of black anti-rust agent and sufficient black tone.Anticorrosive metal part of the present invention, such as can be automobile metal molding, metal formed article etc. for civil construction.As automobile metal molding, it can be specifically web member of various tabular molding, screw, bolt, nut, packing ring etc. etc., as civil construction metal formed article, it can be specifically the web member etc. of the screw that uses such as various tabular molding, electric car, bolt, nut, packing ring etc.
Embodiment
Below by embodiment, the present invention will be described in detail, but the present invention is not limited with these examples.
Prepare following metal base test portion 1 and test portion 2 as metal base:
(1) metal base test portion 1:SPCC, 5D steel plate, size: 70 * 150 * 0.8mm
(2) metal base test portion 2: bolt (mild steel system), M10 * 55, pitch 1.5mm, hardness 9T
Embodiment one
Described metal base test portion 1 and test portion 2 are undertaken, after degreasing, by shot-peening, carrying out surface grinding by solvent respectively, complete the pre-treatment of each test portion.
In the deionized water (below 8.00 μ S/cm) of 34.6 mass parts, mix, add γ-Racemic glycidol trimethoxy silicon (CHISSO Co., Ltd. manufacture: S510) as (4) silane coupling agent, together mix of 13.5 mass parts simultaneously.Mentioned component was mixed after 3 hours, NONION NS-204.5), the non-ionic surfactant (HLB13.5) of 1.0 mass parts (Japan Oil Co: NONION NS-208.5) and as additive for coatings subtotal 7.9 mass parts such as defoamer of the appropriate amount of other additive, together mix in this mixture, add the orthoboric acid (Wako Pure Chemical Industries, Ltd.'s manufacture) of 0.8 mass parts, the non-ionic surfactant (HLB9.5) of 1.0 mass parts (Japan Oil Co:.In this mixture, now add the dipropylene glycol (ASAHI GLASS Co., Ltd. manufactures, is called for short " DPG ") of 11.4 mass parts as (5) alcohol series solvent.TAROX ETB-300) and as phosphoric acid, be tripolyphosphate zinc (KIKUCHI COLOR Co., Ltd.: ZP-SB) of 3.2 mass parts of rust-stabilising pigment (titanium Industrial Co., Ltd manufactures: in this mixture, to add the zinc pigment (Mitsu Mining & Smelting Co., Ltd's manufacture) of 22.0 mass parts, the black synthetic iron oxide of 7.4 mass parts again.Subsequently, use dismission type whipping appts that above-mentioned all the components is fully mixed approximately 3 hours.Modulating like this zinc is black anti-rust agent.
Described zinc pigment (Mitsu Mining & Smelting Co., Ltd's manufacture) is the zinc powder of manufacturing by distillation method to be formed to the sheet composition of thick 0.1～0.8 μ m (average approximately 0.3 μ m), major diameter size 10～20 μ m.In addition, (titanium Industrial Co., Ltd manufactures described black synthetic iron oxide: ETB-300), particle footpath is that 0.1～0.4 μ m (producer's products catalogue value), specific surface area are 4～8mg
2/ g (producer's products catalogue value).
Using metering bar coater (bar coater) is (No.10) described in black anti-rust agent is coated in, to have completed on the metal base test portion 1 of pre-treatment by the zinc of modulation in the manner described above, dry certain hour (10 minutes), subsequently burn-back certain hour (30 minutes) at 330 ℃ at 100 ℃.Described coating engineering, dry engineering and burn-back engineering are repeated 2 times, and making the final leather film thickness forming is 5～10 μ m.Manufactured like this anti-rust metal base material test portion 1 that is formed with antirust epithelium.In addition, the leather film thickness of measuring by electromagnetic type film thickness gauge is 7.1 μ m.
In addition, by 5 metal base test portions 2 that completed described pre-treatment, at described zinc, be to flood in black anti-rust, on the surface of metal base test portion 2, applying described zinc is black anti-rust agent, final coating amount is with 220～260mg/dm
2for target, dry certain hour (10 minutes) at 100 ℃ subsequently, then at 330 ℃ burn-back certain hour (30 minutes).Above-mentioned engineering is repeated 2 times.Manufacture like this 5 anti-rust metal base material test portions 2 that are formed with antirust epithelium.Average coating amount on these anti-rust metal base material test portions 2 is 230mg/dm
2.In addition, coating amount (mg/dm
2) be the value according to { (the test portion weight after processing)-(weight before test portion is processed) }/(test portion area) calculates.In addition, the area of M10 bolt is according to the account form of bolt manufacturer, and use mean value is 23.6dm
2bolt.
Embodiment 2～9
Change in the combination shown in table 1, same with embodiment one, manufactured respectively anti-rust metal base material test portion 1 and 5 anti-rust metal base material test portions 2.
[table 1]
Manner of comparison 1～35
Change in the combination shown in table 2～4, same with embodiment one, manufactured respectively anti-rust metal base material test portion 1 and 5 anti-rust metal base material test portions 2.
[table 2]
[table 3]
[table 4]
Like this, by fluorescent x-ray, analyze, each composition of " antirust overlay film " in the described anti-rust metal base material test portion 1 obtaining respectively in embodiment 1～9 and manner of comparison 1～35 is carried out quantitatively.From this measurement result, calculate mass ratio (1)/(2) and mass ratio (2)/(3) in " antirust epithelium ".In addition, by electromagnetism mould meter (manufacture of FISCHER company), the thickness of the antirust overlay film of described anti-rust metal base material test portion 1 is measured.Coating amount in described anti-rust metal base material test portion 2 calculates by above-mentioned calculating formula.In addition, in table 2～4, when not containing described composition (2) or (3), by described mass ratio (1)/(2) or mass ratio (2)/(3) with " 100/0 " mark.These results and described measurement result one are coexisted in table 1～4 and indicated.
Respectively the described anti-rust metal base material test portion 1 obtaining by embodiment 1～9 and manner of comparison 1～35 is implemented " black tone test ", described anti-rust metal base material test portion 2 is implemented to " salt spray testing ", carry out comprehensive evaluation.
As the black tone test of black tone, use the metal base test portion 1 that is formed with the antirust overlay film with 5～10 μ m thickness, the L value in " black tone " recorded by JIS K 5600-4-6 (1999) is carried out form and aspect mensuration.The aberration using is counted the manufacture of Minolta company, model " CR-300 ".Determined L value minute 4 stages are evaluated, in table 1, with mark, indicated.
◎: L value is less than 10 (L < 10)
Zero: L value is more than or equal to 10 and is less than 40 (10≤L < 40)
△: L value is more than or equal to 40 and is less than 50 (40≤L < 50)
*: L value is more than or equal to (50≤L)
As the salt spray testing of rustless property, " salt spray testing " with JIS K 5600-7-1:1999, recorded is as the criterion and implements.Measure to the time producing till red rust, this time is divided into 4 stages and evaluates, in table 1, with mark, indicate.
◎: at the red rust of more than 1000 hours (containing 1000 hours)～generation in 1500 hours
Zero: in more than 750 hours (containing 750 hours)～less than, within 1000 hours, produce red rust
△: produce red rust for 750 hours in more than 500 hours (containing 500 hours)～less than
*: in less than, within 500 hours, produce red rust
According to " black tone " of such evaluation and " salt spray testing ", according to following standard, the result of comprehensive evaluation is indicated with mark in table 1.
◎: salt spray testing be evaluated as the test of ◎, black tone be evaluated as △ when above
Zero: salt spray testing be evaluated as zero, black tone test be evaluated as △ time
*: the evaluation of the evaluation of salt spray testing or black tone test have at least one for * time or, the evaluation of salt spray testing or the evaluation of black tone test be while being △
Mass ratio (2)/(3) that the result of salt spray testing obtaining like this and mass ratio ((1)/(2)), described (2) black synthetic iron oxide and described (3) phosphoric acid of described (1) zinc pigment and/or zinc alloy pigment and described (2) black synthetic iron oxide are rust-stabilising pigment are associated, and arrange as table 5.
[table 5]
In addition, mass ratio (2)/(3) that are rust-stabilising pigment by obtained black tone test-results and mass ratio ((1)/(2)), described (2) black synthetic iron oxide and described (3) phosphoric acid with described (1) zinc pigment and/or zinc alloy pigment and described (2) black synthetic iron oxide are associated, and arrange as table 6.
[table 6]
As shown in table 1, table 5 and table 6, the embodiment 1～9 that contains special component with specific mass ratio, its rustless property and black tone test are all good.
In addition, as shown in table 2～table 6, in manner of comparison 1～35, do not contain specific composition, or, even if contain special component, its composition beyond the scope of specific mass ratio, thereby its rustless property or black tone have at least one not ideal enough.In addition, use carbon to substitute black synthetic iron oxide in manner of comparison 35, its rustless property is undesirable.
Claims (7)
1. zinc is a black anti-rust agent, it is characterized in that:
Contain,
(1) zinc pigment and/or zinc alloy pigment; (2) black synthetic iron oxide; (3) phosphoric acid is rust-stabilising pigment,
Wherein,
The mass ratio of described (1) zinc pigment and/or zinc alloy pigment and described (2) black synthetic iron oxide ((1)/(2)) is 85/15～65/35,
Described (2) black synthetic iron oxide and described (3) phosphoric acid are that the mass ratio ((2)/(3)) of rust-stabilising pigment is 70/30～50/50,
And, do not contain carbon.
2. zinc according to claim 1 is black anti-rust agent, it is characterized in that, contains:
(4) silane coupling agent and/or titanium couplant; (5) alcohol series solvent.
3. an antirust epithelium, is characterized in that:
Contain,
(1) zinc pigment and/or zinc alloy pigment; (2) black synthetic iron oxide; (3) phosphoric acid is rust-stabilising pigment,
Wherein,
The mass ratio of described (1) zinc pigment and/or zinc alloy pigment and described (2) black synthetic iron oxide ((1)/(2)) is 85/15～65/35, described (2) black synthetic iron oxide and described (3) phosphoric acid are that the mass ratio ((2)/(3)) of rust-stabilising pigment is 70/30～50/50
And, do not contain carbon.
4. antirust epithelium according to claim 3, is characterized in that:
Contain (4) silicon oxide and/or titanium oxide.
5. according to claim 3 or antirust epithelium claimed in claim 4, it is characterized in that:
Be to be that black anti-rust agent is dry at 70～120 ℃ by claim 1 or zinc claimed in claim 2, and burn-back form at 250～360 ℃.
6. an anticorrosive metal part, is characterized in that:
On the surface of metal base, there is the antirust epithelium described in any one of claim 3～5.
7. anticorrosive metal part according to claim 6, is characterized in that:
Described antirust epithelium has the thickness of 5～20 μ m.
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| JP2009-102778 | 2009-04-21 | ||
| JP2009102778 | 2009-04-21 | ||
| PCT/JP2010/002798 WO2010122756A1 (en) | 2009-04-21 | 2010-04-16 | Zinc-based black rust inhibitor, rust inhibiting coating film, and rust inhibiting metal member |
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| JPH0696776B2 (en) * | 1985-08-07 | 1994-11-30 | 日新製鋼株式会社 | Colored surface-treated steel sheet with excellent scratch resistance, adhesion and lubricity |
| JP3259976B2 (en) | 1992-03-13 | 2002-02-25 | 株式会社放電精密加工研究所 | Metal anticorrosive |
| JPH0649393A (en) | 1992-07-30 | 1994-02-22 | Nippon Oil & Fats Co Ltd | Black zinc dust coating composition |
| US5558705A (en) * | 1994-10-31 | 1996-09-24 | Silberline Manufacturing Co., Inc. | Colored metallic pigments |
| US5868819A (en) | 1996-05-20 | 1999-02-09 | Metal Coatings International Inc. | Water-reducible coating composition for providing corrosion protection |
| JPH1068085A (en) | 1996-08-28 | 1998-03-10 | Nippon Rasupaato:Kk | Coating material for iron ground or surface treatment of iron ground or surface treatment of fastened parts |
| JP3394876B2 (en) * | 1996-12-26 | 2003-04-07 | 三井金属塗料化学株式会社 | Black paint composition containing zinc dust |
| JP2000239570A (en) * | 1999-02-25 | 2000-09-05 | Kansai Paint Co Ltd | Corrosion-proofing coating composition |
| JP2001303279A (en) | 2000-02-17 | 2001-10-31 | Toyo Gurahoiru:Kk | Self-sacrificial metal corrosion preventive agent and metal corrosion preventive method |
| JP3938352B2 (en) * | 2001-11-05 | 2007-06-27 | アイシン化工株式会社 | Zinc powder-containing slurry and water-based coating material |
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