CN100507075C - Surface-treated, zinc-plated steel sheet having excellent resistance to tape peeling, method for producing same, and surface treatment agent - Google Patents
Surface-treated, zinc-plated steel sheet having excellent resistance to tape peeling, method for producing same, and surface treatment agent Download PDFInfo
- Publication number
- CN100507075C CN100507075C CNB2004800164400A CN200480016440A CN100507075C CN 100507075 C CN100507075 C CN 100507075C CN B2004800164400 A CNB2004800164400 A CN B2004800164400A CN 200480016440 A CN200480016440 A CN 200480016440A CN 100507075 C CN100507075 C CN 100507075C
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- Prior art keywords
- layer
- steel plate
- treatment agent
- surface treatment
- resistance
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- Expired - Lifetime
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- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- BHRZNVHARXXAHW-UHFFFAOYSA-N sec-butylamine Chemical compound CCC(C)N BHRZNVHARXXAHW-UHFFFAOYSA-N 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 235000012976 tarts Nutrition 0.000 description 1
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 1
- ZISSAWUMDACLOM-UHFFFAOYSA-N triptane Chemical compound CC(C)C(C)(C)C ZISSAWUMDACLOM-UHFFFAOYSA-N 0.000 description 1
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Abstract
A surface-treated, zinc-plated steel sheet is disclosed in which at least a surface modification layer and a coating film are formed on a zinc-plating layer of a zinc-plated steel sheet. The surface modification layer contains, in terms of Si, 1-30 mg/m<2> of SiO2, 0.5-15 mg/m<2> of P and 0.4-10 mg/m<2> of Al. The surface-treated, zinc-plated steel sheet is a non-chromate treated steel sheet, and particularly exhibits excellent resistance to tape peeling even after alkaline degreasing. A method for producing such a surface-treated, zinc-plated steel sheet and a surface treatment agent are also disclosed.
Description
Background of invention
1. invention field
The present invention relates to use the surface-treated steel plate galvanized, more particularly, relate to the steel plate galvanized that is formed with surface-treated layer, wherein the surface-treated layer resistance to tape peeling is good, and resistance to tape peeling still is good after alkaline degreasing, also relates to the manufacture method of steel plate galvanized and is used for the surface-treated surface treatment agent.
2. description of the Prior Art
For the steel plate that is used for household electrical appliance, material of construction and automobile,, use steel plate galvanized usually from corrosion resistant viewpoint.But, be not enough because the zinc type is electroplated when using separately for obtaining erosion resistance (anti-white rust), and, therefore used phosphatizing or chromate treating as countermeasure as being difficult to guarantee bonding with coated material under the situation of undercoat.Although can improve bonding with coating considerably as the phosphatizing of prime treatment, it lacks versatility, because only the effect that suppresses white rust by phosphatizing is poor.
Simultaneously, good although chromate treating suppresses the effect of white rust, bonding insufficient with coating under its processed state.So, bonding in order to improve, and function such as high anti-corrosion, anti-finger printing and oilness also are provided, developed the multifunctional product that on the chromate treating layer, applies the 1 μ m film coating of having an appointment, and mainly be used in usually in the household electrical appliance manufacturing.
But because chromate treating uses deleterious sexavalent chrome, so it involves and causes public pollution problems, and chromate treating is often because account for dominant position and the environmental protection requirement that increases day by day and being avoided.So, proposed not use the surface treatment (non-chromate method) of chromate treating in a large number and come into operation.
For example, JP-A No.8-325760 discloses the surface treatment agent of the steel plate that is used to plate zinc-containing metal, this treatment agent uses the blend compositions of water soluble resin and polyphenol carboxylic acid, and discloses by treatment agent is rolled onto and be coated with the good surface-treated steel plate of solidity to corrosion that forms on the metallic surface.But, in this technology, omitted chromate treating, so coating is bonding insufficient owing to zinc coating directly applies organic layer.In addition, although the steel plate galvanized of handling for the clean sheet confronting surfaces has carried out alkaline degreasing, promptly be coated in the bounding force that lip-deep oil improves coating by removing in the process such as compacting, it reduces corrosion proof problem after relating to alkaline degreasing.
As improvement to this class problem, JP-A No.2000-144448 disclose by on steel plate galvanized directly coating contain the organic layer of ion-exchange silicon-dioxide or utilize the prime treatment layer such as layer that lithium silicate or Trilithium phosphate are handled forms and is coated with the steel plate of organic material, thereby improved the solidity to corrosion after solidity to corrosion, the alkaline degreasing and the binding property of coating.
In addition, JP-A No.2000-144444 discloses the good surface treated steel plate of solidity to corrosion of the chemical conversion coating that is formed with pre-determined thickness, be by with the silicon-dioxide or silicon dioxide gel, phosphate cpd, the oxide compound of specified metal or the acidic treatment solution of oxyhydroxide that comprise preferred proportion steel plate galvanized being applied processing, by heating its drying being obtained then.But, because dry then with inorganic agent such as silicon dioxide gel, phosphoric acid salt or metal hydroxides coating and keep under the state of its former state be easy to form pin hole etc. in layer, so corrosive liquid may be invaded pin hole and be made solidity to corrosion insufficient when alkaline degreasing etc.In view of the foregoing, in this patent documentation, on chemical conversion processing layer, form organic resin layer or organic composite silicate layer with the solidity to corrosion after improving alkaline degreasing or the binding property of coating.
Simultaneously, JP-A No.2000-129460 discloses the surface treated steel plate of solidity to corrosion and the raising of coating binding property, by following formation: form Zn-based plating layer as the first layer, mixed aqueous solution by coating and dry polyvalent metal uncle's phosphoric acid salt and metal oxide sol forms amorphous coating as the second layer, with inorganic coating as the 3rd layer, form multilayered structure thus.
In addition, JP-A No.2001-11645 discloses the steel plate that scribbles organic materials that the binding property by the following solidity to corrosion that obtains, solidity to corrosion after the alkaline degreasing and coating improves: the thin SiO that comprises that forms pre-determined thickness on the surface of steel plate galvanized
2The composite oxide layer of particle and phosphate compounds is as the first layer; And on the first layer, form the organic polymer that has OH group or COOH group comprising of pre-determined thickness organic material layer as base resin.
In addition, JP-A No.2003-293151 discloses non-chromate type surface-treated steel plate galvanized, and it is formed with predetermined proportion and comprises each surface reforming layer of Al, Si and P, and this steel plate shows the solidity to corrosion that can compare with the steel plate of chromate treating.
As mentioned above, in non-chromate is handled, proposed the various improvement technology of several themes, and tested the various improvement of performance.But,, also relate to the insufficient serious problems of resistance to tape peeling even obviously used the steel plate galvanized that improves the non-chromate processing according to the inventor's nearest experience.
That is to say that the surface-treated steel plate betransported with the form of band steel bundle volume, the user uses them as shear plate after untiing their.In this case, sometimes by temporarily fixing the residue volume that bringing in of volume stores after using with adhesive tape.In addition, utilize step such as punching press, oily coating, press forging and alkaline degreasing that the plate of shearing is manufactured AV product box or part.In this case, the adhesive-stick type label of indication number of spare parts, size, grade etc. is attached to sometimes on the surface of case or part and is used for working fastening.Band peel off for the top coat on the galvanizing surface when user's stripping tape or the adhesive-stick type label with being with the phenomenon of peeling off from plate surface.Consider the quality of surface-treated steel plate, this is a crucial problem, and may cause serious product defects.
Band is peeled off to be applied with in the conventional chromate treating type surface treated steel plate of film coating at top layer and is taken place hardly, therefore, does not recognize " band the is peeled off improvement " problem that is used to prevent with peeling off so far.
By the way, in the improved research process of non-chromate type steel plate galvanized that the inventor carries out, obviously, the good or poor situation that depends on non-chromate surface-treated steel plate of resistance to tape peeling.Especially, obviously, long-time store tape from the teeth outwards simultaneously or the situation of label under or under situation about storing under high temperature and the high humidity, be easy to take place band in the hypothesis sea transport and peel off.So, recognize that " resistance to tape peeling " is extremely important product performance.
But,, therefore also just can not recognize the problem of " resistance to tape peeling improvement " owing to problem that " band is peeled off " is own is not almost being recognized at present.For countermeasure,, in fact, also do not work out practical method equally for the disclosed technology of above-mentioned non-chromate processing type electroplating steel plate remains inadequate.
Summary of the invention
In this case, the present invention relates to non-chromate surface-treated steel plate galvanized, and aim to provide the good surface-treated steel plate galvanized of resistance to tape peeling after resistance to tape peeling and the alkaline degreasing, its manufacture method and be used for the surface treatment agent of manufacture method.
The one aspect of the present invention that addresses the above problem is the surface-treated steel plate galvanized, and this steel plate galvanized has at least one surface reforming layer and the top coat that forms on the steel plate galvanized Zn-based plating layer, and wherein surface reforming layer comprises that to be converted into Si be 1-30mg/m
2SiO
2, 0.5-15mg/m
2P and 0.4-10mg/m
2Al.
Another aspect of the present invention is to be used to obtain the SiO that contains of the good steel plate galvanized of resistance to tape peeling
2The phosphate type surface treatment agent, wherein the concentration of solids content is 0.01-14.5% (here and hereinafter for quality %), the Si that comprises in the treatment agent, P and Al quantity and proportion of composing (mass ratio) separately meets the following conditions:
Si：0.002-4.5％
P：0.0005-1.5％
Al：0.0001-0.5％
1.5≤Si/P≤60，4.5≤Si/Al≤230
One aspect of the present invention is to make the method for surface-treated steel plate galvanized, this method comprises uses the surface treatment agent that satisfies above-mentioned condition to form the surface treatment agent layer on the surface of steel plate galvanized, should wash with water, from the surface treatment agent layer, remove excessive P and/or Al whereby, the dry then surface reforming layer that forms.
The accompanying drawing summary
Fig. 1 is the FT-IR spectrum of the surface reforming layer of following No.38.
Fig. 2 is the FT-IR spectrum of the surface reforming layer of following No.52.
Fig. 3 has shown the FT-IR spectrum of sodium polyacrylate.
DESCRIPTION OF THE PREFERRED
Surface-treated steel plate galvanized according to the present invention is based on the prerequisite with the surface reforming layer that forms by the non-chromate treatment agent.Be applicable to that steel plate galvanized of the present invention can comprise the steel plate that only is coated with zinc, and the steel plate of all other galvanized alloys, as the steel plate of zinc-plated-Ni, zinc-Fe, zinc-Al.In addition, equally for method for plating, can adopt any in fusion method for plating, electro-plating method or the vapour deposition method for plating.
Notable feature of the present invention is to mix that to be converted into Si be 1-30mg/m in surface reforming layer
2SiO
2, 0.5-15mg/m
2P and 0.4-10mg/m
2Al, as the means that improve " resistance to tape peeling ", this is that the inventor at first proposes the new problem that solves in non-chromate steel plate galvanized field.
" resistance to tape peeling " is meant in the present invention sticking Adhesive Label or adhesive tape and pastes and be retained in and peel off then on the surface-treated steel plate galvanized under their situation, can not cause this anti-separability that surface-treated layer is peeled off with them.The degree of resistance to tape peeling is different, depends on the kind that is used to the adhesive tape of stripping test, the solvent that particularly wherein comprises or the binding property of softening agent or kind.
Consider that maximum reason that top layer resin layer or surface reforming layer are peeled off because of band is attributable to the solvent that comprises in the tackiness agent or softening agent diffusion and infiltration and goes up the surface of the top layer of formation up to Zn-based plating layer by surface reforming layer and its, and gather the bonding border that reduces cohesive strength, thereby resistance to tape peeling can change considerably with the kind and the content of solvent that comprises in the adhesive tape or softening agent.
But,, think their diffusions or be penetrated into particularly SiO although be mixed into the kind of solvent in the adhesive tape commonly used or softening agent and mix quantity and can change to a certain extent as tackiness agent
2The speed of inclusion does not have marked difference.So, shown in the embodiment as described below, in the present invention, when selecting and use (as exemplary) silk ribbon " the Part No. #9510 that Surion Tech Co makes " and " " glass paper tape " that Nichiban Co. makes ", estimate resistance to tape peeling as the preliminary assessment standard.
Silicon-dioxide (SiO as main component in the surface reforming layer of the present invention
2) the Si oxide that mixes therein for for example obtaining from colloidal silica or silicate.Because above-mentioned silicon-dioxide person's character is inorganic materials, and have good affinity with Zn-based plating layer, therefore when it forms the bottom of top layer, it can provide the effect of the anti-stripping performance between enhancing Zn-based plating layer and the top layer.
As mentioned above, a reason peeling off of band is considered to by the interface between kinetic each layer of solvent that comprises in the tackiness agent of diffusion component such as adhesive tape etc. and softening agent or the reduction of boundary cohesive strength.But, think that the silicon-dioxide that comprises as main component can provide spreading and the solvent of infiltration and the superior barrier effect of softening agent from top layer in surface reforming layer of the present invention, and provide inhibition to invade the function of galvanizing surface, or be suppressed at the function of top layer or the diffusion of surface reforming layer boundary.Therefore, when the surface-treated layer of silicon-dioxide of sufficient quantity was mixed in formation, resistance to tape peeling was significantly improved.So,,, confirm by being 1-30mg/m being converted into Si in the control surface processing layer according to the result that the inventor studies its quantitative association for the effect that effectively provides silicon-dioxide to improve resistance to tape peeling
2Dioxide-containing silica (2.14-64.3mg/m
2SiO
2) can provide good resistance to tape peeling in the scope.
Be converted into Si less than 1mg/m at dioxide-containing silica
2Situation under, just insufficient as the effect on above-mentioned blocking layer, and be difficult to the resistance to tape peeling that provides satisfied.Therefore, the dioxide-containing silica in the surface reforming layer is converted into Si and is necessary for 1mg/m
2Or more than.The lower limit of dioxide-containing silica is preferably 2mg/m
2, more preferably 2.5mg/m
2
So, when dioxide-containing silica increases, be enhanced, but when dioxide-containing silica excessively increased, resistance to tape peeling was tending towards reducing on the contrary as the effect on blocking layer.That is to say, think that the silicon-dioxide in the surface-treated layer exists with fine grain aggregate under the little state of its quantity, but when silicon-dioxide quantity increased, fine particle may become multilayer laminated state.Because it is not always very strong in the cohesive strength between each fine silica granular layer under the multilayer laminated state, therefore with peeling force being applied under the multilayer laminated state on the direction of peeling off the fine silica granular layer, cause the splitting of fine silica granular layer thus.For the splitting that the shear fracture that suppresses as far as possible by surface reforming layer itself causes, the dioxide-containing silica in the surface reforming layer is converted into Si should remain on 30mg/m
2Or lower, the dioxide-containing silica in surface reforming layer surpasses under the situation of higher limit, and resistance to tape peeling obviously shows reduction trend.In addition, the excessive increase of dioxide-containing silica is seen also from economic angle and is wasted in the surface reforming layer, and in view of foregoing, the upper limit that is converted into Si is preferably 15mg/m
2, more preferably 10mg/m
2, 8mg/m most preferably
2
In silica containing surface reforming layer of the present invention, also comprise P and Al.In preparation during surface reforming layer, the surface of preferred etching Zn-based plating layer, and the fine silica particle that deposition is obtained by colloidal silica etc. on the surface of the suitable coating of roughen.The spendable etching composition of this paper is for example nitric acid, sulfuric acid, hydrochloric acid and phosphoric acid.Especially preferred use comprise aluminium salt such as phosphoric acid salt, hydrophosphate, phosphite or phosphorous acid hydrogen salt (hereinafter being called the aluminate or phosphate compound simply) as the acidic aqueous solution of etching composition as surface-modifying agent, in acidic aqueous solution, also be dispersed with the colloidal silica of sufficient quantity.Therefore, in the surface reforming layer that obtains, comprise P and Al.
The acidic aqueous solution that comprises colloidal silica and aluminate or phosphate compound when use is during as surface treatment agent, and the surface of Zn-based plating layer is wherein mainly comprised being difficult for molten AlPO in the aluminate or phosphate by the acidic aqueous solution etching
4Or Al
2(HPO
4)
3The responding layer (surface reforming layer) of (not soluble in water or alkaline aqueous solution) is formed on the surface of Zn-based plating layer.When the fine silica particle was deposited and absorbs in the responding layer, aluminate or phosphate and fine silica particle were by compound and become integral body.And, with regard to regard to the Zn-based plating layer of etching roughening, having formed fine and close responding layer, it combines with the top layer that forms thereon, and this top layer also is fine and close and strong, thus resistance to tape peeling is significantly improved.In addition, as hereinafter describing, when organic resin aqueous solution is incorporated in the acidic aqueous solution, can make the fine silica particulate deposition attitude in the surface-modifying agent that obtains stronger.
Owing to wherein mainly comprise and be difficult for molten AlPO
4Or Al
3(HPO
4)
3Aluminate or phosphate and the fine silica particle by compound and become whole responding layer and have better alkali resistance than by the surface reforming layer that for example uses nitric acid to obtain as etching reagent, so it can also provide the excellent resistance to tape peeling performance after the alkaline degreasing.But, by using above-mentioned aluminate or phosphate compound to form under the situation of silica containing surface reforming layer as etching composition, find that alkali resistance or resistance to tape peeling after the alkaline degreasing are different, depend on the P and the Al content separately that comprise in the surface reforming layer.Especially, recognize when the thickness of surface reforming layer increase and layer in the quantity of aluminate or phosphate when increasing, the resistance to tape peeling after the alkaline degreasing often reduces.
Under the thin situation of surface reforming layer, because surface reforming layer and Zn-based plating layer are close to each other, so zinc leaches the H in the treatment agent by the etching of Zn-based plating layer
+Be reduced into H
2Gas, thus increase and often become alkalescence near near the pH the surface reforming layer of Zn-based plating layer.In the atmosphere that pH increases greatly, numerous Al PO
4Or Al
2(HPO
4)
3Be formed responding layer, wherein be difficult for molten aluminate or phosphate and fine silica particle, significantly improved the resistance to tape peeling after resistance to tape peeling and the alkaline degreasing by compound and become integral body.But, when the thickness of surface reforming layer increases, because the surface of the surface reforming layer that is just forming and Zn-based plating layer are more and more far away from getting each other, therefore the influence of the pH that leaches with zinc applies less, the atmosphere of surface reforming layer near surface becomes surface treatment agent inherent acidity, thereby often forms than being difficult for molten AlPO
4Or Al
2(HPO
4)
3More Al more soluble in water
2(HPO
4)
3(being easier to be subjected to alkali corrodes).Think as water-soluble Al
2(HPO
4)
3During with the relatively large outmost surface that is present in surface reforming layer, because water soluble component leaches from surface reforming layer when standing alkali and corrode, so the alkali resistance of surface-modifying agent reduces the resistance to tape peeling reduction after the alkaline degreasing.
But in the present invention, the thickness by the defining surface modified layer is to pre-determined range and limit that P and Al quantity separately can obtain stable excellent resistance to tape peeling and the resistance to tape peeling after the alkaline degreasing to pre-determined range in the layer.Therefore, in the essential in the present invention control surface modified layer content of P at 0.5-15mg/m
2Scope in and the content of Al at 4.0-10mg/m
2Scope in.At the content of P less than 0.5mg/m
2Or the content of Al is less than 0.4mg/m
2Situation under, etch effect is inadequate, and seldom forms fine and close responding layer, in addition, can not effectively provide sometimes by improving the effect that the fine silica particle deposition improves resistance to tape peeling.P content more preferably be limited to 0.6mg/m down
2, Al content more preferably be limited to 0.5mg/m down
2On the contrary, when P content or Al content excessively increase, as mentioned above, in surface reforming layer, introduce the inadequate Al (H of alkali resistance
2PO
4)
3, and often under alkali corrodes, from surface reforming layer, leach.The preferred upper limit of P content is 9mg/m
2, be limited to 7.2mg/m on it is preferred
2, be limited to 5mg/m on most preferred
2The preferred upper limit of Al content is 8mg/m
2, be limited to 6.3mg/m on it is preferred
2, be limited to 4.4mg/m on it is most preferred
2
In addition, the Si that comprises in surface reforming layer, P and Al content separately satisfies under the situation of following relationship formula (1) and (2):
0.5≤Si/P≤20 (1)
0.7≤P/Al≤6 (2)
Can guarantee better resistance to tape peeling and the resistance to tape peeling after the alkaline degreasing.
When Si/P less than 0.5 the time, because SiO in the surface reforming layer
2Ratio be tending towards insufficient relatively, so resistance to tape peeling is tending towards reducing.On the other hand, when ratio surpasses 20, because the quantity of aluminate or phosphate is insufficient with respect to the content of silicon-dioxide, therefore by being difficult for molten AlPO
4Or Al
2(HPO
4)
3It is not too effective that the effect that obtains becomes.From the above point of view, in the surface reforming layer Si/P ratio more preferably be limited to 1 down, be limited to 15 on more preferably, be limited to 10 on more preferably.
P/Al in relational expression (2) less than 0.7 situation under, resistance to tape peeling is often owing to coming from insufficient reduction of the insufficient etching of phosphoric acid.On the other hand, when the excessive increase of ratio surpassed 6, what form after the etch processes was difficult for molten AlPO
4Or Al
2(HPO
4)
3Quantity reduce, make it be not enough to form fine and close responding layer, and the effect that improves the resistance to tape peeling after the alkaline degreasing reduces.Therefore,, guarantee suitable etch effect simultaneously by control P/Al to 0.7 or higher and 6 or the lower formation that promotes to be difficult for molten aluminate or phosphate, thus formation capacity responding layer.P/Al more preferably is limited to 1 down, and it is limited to 4 on more preferably.
Can be by the content of silicon-dioxide, silicate, phosphate composition and Al composition in the control surface treatment agent, or when forming surface reforming layer, wash and remove the excess phosphoric acid composition with flushing or Al becomes to assign to control Si/P or P/Al, this describes hereinafter.In addition, can be by the quantity of Si, P and Al in the identified surface modified layer respectively of fluorescent X-ray analysis for example.
When except in surface reforming layer, mixing the silicon-dioxide, also mix the P and the Al of pre-determined quantity separately, and when also controlling Si, P and Al the ratio of content be to optimum range separately, can make the surface reforming layer that obtains finer and close, do not have needle pore defect etc., and show outstanding resistance to tape peeling performance under the condition of doing and the resistance to tape peeling after the alkaline process de-oiling.
In the present invention, also can in surface reforming layer, mix organic resin.This is to make the fine silica particle firmly be deposited on effect in the surface reforming layer when forming surface reforming layer because organic resin has, and further improves the resistance to tape peeling after resistance to tape peeling and the alkaline degreasing.Organic resin is not particularly limited, can comprise for example acrylic resin, melamine resin, resol, Resins, epoxy, urethane resin, vibrin, Synolac and polyolefin resin, they can use separately, or are used in combination in them two or more.
In above-mentioned organic resin, preferably use water-soluble organic resin, the organic resin that especially preferably uses organic acid to constitute.For the organic resin that organic acid constitutes, poly--(methyl) vinylformic acid is suitable, can use wherein acid groups partly or entirely used the alkali neutral those.As mentioned above, when forming surface reforming layer, preferably by using acidic aqueous solution etching zinc coating.Because comprising organic acid almost is water miscible as the organic resin of moiety, and the aqueous solution that comprises this organic resin is tart, but therefore stable and practicality excellence when mixes with acidic aqueous solution.During use, poly-(methyl) acrylic acid molecular-weight average be preferably 2000 or more than, more preferably 10000 or more than, also preferred 100000 or more than.Under the situation of the salt of the organic resin that uses organic acid to form, alkali can comprise for example ammonia or alkali-metal oxyhydroxide, as sodium hydroxide or potassium hydroxide.
When for example observing surface reforming layer by FT-IR, appear in the spectrum owing to come from the FT-IR peak of organic resin structure (ester bond, base, ketone, amino, hydroxyl and C-H etc.), but the therefore existence of organic resin in the identified surface modified layer.So, in the present invention, preferably exist organic resin to make that the FT-IR specific absorption that comes from the organic resin structure is 0.1-15.The content of organic resin in the FT-IR specific absorption presentation surface modified layer can improve resistance to tape peeling after resistance to tape peeling and the alkaline degreasing by control FT-IR specific absorption to definite scope.
The present invention also comprises the surface treatment agent that is used to form surface reforming layer.Surface treatment agent is the phosphate type treatment agent, for comprising as the fine grain solution form of the silicon-dioxide of colloidal silica, preferred control makes that solids concn is 0.01-14.5 quality %, the quantity of the Si that comprises in the treatment agent, P and Al (quality % hereinafter simply is called %) and sets of numbers proportional (mass ratio) can meet the following conditions:
Si：0.002-4.5％
P：0.0005-1.5％
Al：0.0001-0.5％
1.5≤Si/P≤60，4.5≤Si/Al≤230。
When the solids concn of surface treatment agent less than 0.01% the time, be difficult to form surface reforming layer by primary treatment with satisfied thickness, it is essential repeatedly handling, this makes it impracticable.On the contrary, if excessive concentration surpasses 14.5%, then often the gas/liquid boundary in treatment agent for example forms solid, and this often causes product defects such as impression or seed crystal.In view of foregoing, solids concn be preferably 0.05% or more than and 10% or below, and more preferably 0.1% or more than and 0.5% or below.
In addition, the Si concentration in surface treatment agent is less than under 0.002% the situation, often becomes inadequately as the content of the silicon-dioxide of blocking layer main ingredient in the surface reforming layer, thereby is difficult to obtain gratifying resistance to tape peeling.On the other hand, when Si concentration surpassed 4.5%, the content of silica ratios excessively increased in the surface treatment agent, make that the content of silicon-dioxide is excessive in the surface reforming layer, so resistance to tape peeling was tending towards more reducing.In view of above-mentioned trend, the lower limit of Si concentration more preferably 0.01% in the surface treatment agent, and more preferably 0.03%.In addition, the upper limit more preferably 4%, more preferably 3%.In addition, can be mainly according to as colloidal silica blended SiO
2Combined amount and and the combined amount of silicate etc. come Si concentration in the control surface treatment agent.
The colloidal silica that can mix as silica source in the surface treatment agent for example can preferably include " SNOWTEX " series (colloidal silica, Nissan Chemical Industry Co. production) " O ", " OS ", " OL ", " OXS " and " OUP " in, silicate is preferably Na
4SiO
4Or Na
2SiO
3
On the other hand, the concentration of P depends on the quantity of the phosphate compounds of sneaking into as phosphoric acid salt, hydrophosphate, phosphite or phosphorous acid hydrogen salt in the surface treatment agent, and it is the important factor that major control etch effect and fine and close responding layer form.Under the low excessively situation of the concentration of P, because etching action is insufficient, the formation of above-mentioned fine and close aluminate or phosphate type responding layer also is not enough to reduce the effect that promotes the fine silica particle deposition, and the binding property of surface reforming layer or alkali resistance often become insufficient.Therefore, the concentration of P preferred 0.0005% or higher in the treatment agent.More preferably be limited to 0.001% down, be limited to 0.01% under preferred.
But, when the concentration excess of P in the surface treatment agent increases,, and consider actually operating, the problem that it also causes the surface treatment agent groove often to be corroded easily, therefore preferred 1.5% or still less because product appearance often becomes unhappy.Be limited to 1% more preferably, be limited to 0.5% on preferred.
In addition, the concentration of Al depends primarily on the aluminium salt quantity of aluminium salt such as phosphoric acid in the surface treatment agent, also depends on the quantity of the oxyhydroxide of the oxyhydroxide that can choose adding wantonly such as Al.Especially, its constitute to form the source that is difficult for molten aluminate or phosphate, and aluminate or phosphate forms fine and close responding layer by phosphoric acid etc. in etching step, strengthen surface-modifying agent binding property or alkali-proof vital role to provide by the deposition that promotes silicon-dioxide.For above-mentioned effect is provided effectively, need the concentration of Al in the treatment agent to be at least 0.0001% or higher, preferred 0.0005%, more preferably to 0.001% or higher.But when the excessive concentration of Al, because solid is located often to form in the solution-air border in treatment soln etc., thereby often causes product defects, as impression or seed crystal, it is reduced to 0.5% or lower.Be limited to 0.4% more preferably, be limited to 0.2% on preferred.
The formation amount of the fine and close responding layer of the aluminate or phosphate that Si/P in the surface treatment agent and Si/Al form to mainly be included in initial surface treatment stage the and influential to the deposition of aforesaid silicon-dioxide.P content and Al content to the insufficient situation of Si content under, etching is insufficient relatively, this makes that the density or the formation amount of the responding layer that mainly comprises aluminate or phosphate are not enough, and has reduced the effect that promotes silica deposit.Therefore, the resistance to tape peeling deficiency after resistance to tape peeling and the alkaline degreasing.On the contrary, when P content and Al content excessively increased with respect to Si content, silica concentration was often not enough in the above-mentioned responding layer, and may cause insufficient resistance to tape peeling.
From the above point of view, the Si/P that comprises in the surface treatment agent is preferably 1.5 or higher and 60 or lower, and more preferably 1.8 or higher and 20 or lower.Si/Al is preferably 4.5 or higher and 230 or lower, and more preferably 6 or higher 100 or lower.
Because bottom is not had particular restriction, so the method for Si, P in the control surface treatment agent and Al content is not had particular restriction.Because Si content depends on the content of silicon-dioxide in the surface treatment agent or silicate respectively, P content depends on phosphoric acid or phosphatic content in the treatment agent, Al content depends on the content of Al phosphoric acid salt in the treatment agent or oxyhydroxide, thus can by respectively suitably in the control surface treatment agent content of mentioned component control the content of various elements.
In addition, comprise at surface treatment agent under the situation of above-mentioned organic resin, with the solid content meter of organic resin, the interpolation concentration of organic resin is preferably 0.01-3g/l in the surface treatment agent.When adding concentration less than 0.01g/l, almost can not get the additive effect of organic resin, on the other hand, when adding concentration above 3g/l, the resistance to tape peeling after the alkaline degreasing may reduce.
In the present invention, especially preferred surface treatment agent is for comprising the acidic aqueous solution of colloidal silica, aluminium salt compound such as aluminate or phosphate, hydrophosphate, phosphite or phosphorous acid hydrogen salt and organic resin (preferred poly-(methyl) vinylformic acid or its salt).When using surface treatment agent, the Zn-based plating layer at surface of steel plate place is etched under acidic aqueous solution, in this process, on the surface of Zn-based plating layer, form and mainly comprise the fine and close responding layer that is difficult for molten aluminate or phosphate, silica deposit on responding layer, and since the effect of organic resin be connected and reliable connection.Therefore, these effects form fine and close responding layer with respect to the zinc that leaches by etching, obtain showing the surface reforming layer of resistance to tape peeling after excellent resistance to tape peeling and the alkaline degreasing.
More specifically, surface treatment agent is preferably this acidic aqueous solution, the colloidal silica of the Al phosphoric acid salt that its solids content that comprises every kind of composition is 0.002-5.0% (more preferably 0.01-1.0%) (or hydrophosphate, phosphite, phosphorous acid hydrogen salt), 0.004-10% (preferred 0.05-3%); And comprising the organic resin of 0.1-3g/l, pH is in the scope of 1.5-4.0.Composition by the defining surface treatment agent and preferably by washing with water etc., can control to the composition of surface reforming layer in the above-mentioned scope in above-mentioned scope.
Method for handle steel plate galvanized with surface treatment agent can comprise any known coating method, for example, can use dip-coating, spraying or roller coat.In dip-coating method, the preferred about 0.1-10 of dip-coating steel plate second.In order to promote the reaction with Zn-based plating layer, spraying method is a method more preferably, and preferred spray pressure is at 20-500kPa (about 0.2-5.0kgf/cm
2) scope in, preferred spray time is in the 0.1-10 scope of second.
Form surface treatment agent layer (forming the layer of surface reforming layer in washing-drying back) with above-mentioned surface treatment agent surface treatment steel plate galvanized after, preferably remove solvable composition by suitable washing.Then, obtain surface reforming layer by for example removing water-content about 30-150 ℃ of following drying in heating.Washing in this step is important treatment step, especially for improving alkali resistance, and therefore improves resistance to tape peeling after the alkaline degreasing of the surface reforming layer that obtains at last.That is to say, the various tests of carrying out according to the inventor, confirm, handling with above-mentioned surface treatment agent under the situation of after drying layer, or under the situation of roasting surface reforming layer, P content or Al content in the surface reforming layer are excessive sometimes, and this content surpasses the 0.5-15mg/m of above-mentioned P in the surface reforming layer
2Preferred content or the 0.4-10mg/m of Al
2Preferred content, therefore becoming is difficult to guarantee resistance to tape peeling after the alkaline degreasing.
That is to say, as described in the preamble prior art, improve by handle galvanized steel sheet surface with the treatment agent that comprises fine silica particle and aluminate or phosphate that corrosion proof method is known after the steel plate galvanized alkaline degreasing, and confirm that also surface treatment is effective as improving the fusible bottom layer treatment of organic top layer.But, the inventor confirms, the surface reforming layer that forms by the surface treatment agent (also comprising those disclosed in the above-mentioned patent documentation) that comprises fine silica particle and aluminate or phosphate comprises quite a large amount of aluminate or phosphate compositions in surface reforming layer, be converted into P and reach about 30mg/m sometimes
2Or more, be converted into Al and reach about 15mg/m
2Or it is higher.So, the inventor finds, when the content of P or Al is big, especially to not very little unwanted influence of the anti-separability after the alkaline degreasing, therefore need wish expediently should wash with water bottom after surface treatment, leaching and remove the water soluble component in the contained aluminate or phosphate in the surface-treated layer whereby in advance (mainly is Al (H
2PO
4)
3), arrive above-mentioned preferable range so that reduce the content of P and Al, thereby form the compact surfaces modified layer that is difficult for molten (alkali resistance is good).
For method for washing, can consider dip-coating or spraying, and can be according to the content appropriate change washing condition of the water soluble component in the aluminate or phosphate composition that comprises in the surface treatment agent layer.Preferably the control washing time is about 0.5-15 second under the dip-coating situation, and the control washing time is that about 0.5-15 second and spray pressure are about 20-500kPa (about 0.2-5kgf/cm under the spraying situation
2), because water soluble component can more effectively be removed.
Lower limit to steel plate galvanized upper surface modified layer deposition does not have particular restriction, and the dry coating after handling for washing is preferably 4.2mg/m
2Or it is higher.When deposition is not enough, owing to be difficult to cover equably the surface of Zn-based plating layer, so resistance to tape peeling is often not enough.The lower limit of deposition is 7mg/m more preferably
2, more preferably 8mg/m
2On the contrary, when it was excessive, the aluminate or phosphate that forms in the surface-treated layer was from being difficult for molten AlPO
4Or Al
2(HPO
4)
3Change into water-soluble Al (H
2PO
4)
3, and the density of responding layer often reduces owing to the undercut of zinc-base plating surface.They have often reduced the resistance to tape peeling after the alkaline degreasing.Therefore, total deposition of surface reforming layer is preferably 130mg/m
2Or still less.The upper limit of deposition more preferably is 65mg/m
2, more preferably 50mg/m
2, 37mg/m most preferably
2Total deposition of surface reforming layer for by for example by Si, P in the fluorescent X-ray analysis quantitative assay surface reforming layer and Al and the value that calculates by deposition, supposition forms SiO when calculating deposition in modified layer
2, AlPO
4, Zn
3(PO
4)
2And Al
2O
3When the preferable range of the deposition of surface reforming layer was roughly represented with layer thickness, it was 0.0021-0.0657 μ m, supposes that proportion is 2.
In surface treatment steel plate galvanized according to the present invention, form aforesaid inherent surface reforming layer of the present invention.In addition, for binding property that characteristic such as solidity to corrosion, anti-finger printing, workability and coating are provided or improve them, on surface reforming layer, directly or by other press the top layer that comprises various organic materialss layer by layer, organic materials such as Resins, epoxy, acrylic resin, polyamide resin, vibrin, Synolac, urethane resin, polyvinyl resin, silicone resin, fluoro-resin and aminoplast(ic) resin.
Wherein, preferably have the surface treatment steel plate galvanized of the resin layer of designated emulsion composition formation as top coat.The emulsion compositions that is used to form resin layer (top coat) comprises that ethylene unsaturated carboxylic acid's multipolymer (also comprise neutral condition those) is as main component, comprising boiling point and be 100 ℃ or lower and quantity is 1 mole of amine that is equivalent to 0.2-0.8mol (20-80mol%) in the carboxyl of ethene-copolymers of unsaturated carboxylic acids, quantity is 1 mole in the carboxyl of ethene-copolymers of unsaturated carboxylic acids, and to be equivalent to the divalent metal compound of 0.02-0.4mol (2-40mol%) and to have two or more to be the linking agent of the 0.5-20 quality % of 100 quality % in the emulsion compositions solids content with the functional group and the quantity of carboxyl reaction.Emulsion compositions does not contain ammonia substantially.
The various excellent propertys of resin layer that obtain by the above-mentioned emulsion composition, but as screening characteristics, oilness and workability and electroconductibility (ground connection property), and the resistance to tape peeling after solidity to corrosion and the oil removing is good, and this discovery is also submitted to Japanese patent application No.2004-30231 by the applicant.
The unsaturated several acid copolymers of ethene are ethene and unsaturated number acid as (methyl) acrylic acid multipolymer.Polymkeric substance can by polymerization as is known the High Temperature High Pressure polymerization process obtain.Multipolymer most preferably is random copolymers, but also can be segmented copolymer, or wherein unsaturated several acid moieties are by the grafted multipolymer.Olefinic monomer such as propylene or 1-butylene can be used as a part of ethene.In addition, other known vinyl monomer can be in the scope that does not hinder the object of the invention by part copolymerization (about 10 quality % or still less).Unsaturated number acid to the copolymerization ratio of ethene be preferably in whole amount of monomer be 100 quality % then unsaturated carboxylic acid be 10-40 quality %.
Because ethene-copolymers of unsaturated carboxylic acids has carboxyl, so its available organic bases or metal ion are by neutralization emulsified (one-tenth water dispersion).In this case, using boiling point is that 100 ℃ or lower amine are as organic bases.When resin coating was dried, boiling point was higher than 100 ℃ amine and often is retained on the steel plate, has increased the water specific absorption of top coat, therefore, has reduced solidity to corrosion or resistance to tape peeling.Therefore, the emulsion compositions that is used to form top coat does not comprise the amine that boiling point is higher than 100 ℃.In addition, owing to do not recognize the influence that adds ammonia, so composition does not comprise ammonia yet.Boiling point is meant boiling point under atmospheric pressure.
Boiling point is that the object lesson of 100 ℃ or lower amine (hereinafter being called amine) can comprise, for example, and tertiary amine such as triethylamine, N, N-dimethyl butylamine, N, N-dimethyl allylamine, N-crassitude, tetramethyl-diamino methane and Trimethylamine 99; Secondary amine such as N-methylethyl amine, diisopropylamine and diethylamine; With primary amine such as propylamine, TERTIARY BUTYL AMINE, sec-butylamine, isobutylamine, 1,2-dibutyl propylamine and 3-amylamine.In mixture, can use one or more amine.Wherein, tertiary amine is preferred, and triethylamine is most preferred.
In the carboxyl in ethene-copolymers of unsaturated carboxylic acids is 1mol, and the quantity of amine is in the scope of 0.2-0.8mol (20-80mol%).At this moment because in above-mentioned scope, solidity to corrosion or resistance to tape peeling are preferred.When the content of amine during less than 0.2mol, the granularity of resin particle increases in the emulsion, and above-mentioned effect can not be provided.On the other hand, when surpassing 0.8mol, the viscosity of emulsion compositions increases, and causes gelation sometimes, and this is not preferred.The upper limit of amine quantity more preferably is 0.6mol, more preferably 0.5mol.Amine quantity more preferably be limited to 0.3mol down.
In order to prepare emulsion compositions, also use monovalent metallic ion.This is effective to improving solvent resistance or film hardness.One divalent metal compound preferably includes one or more metals that are selected from sodium, potassium and lithium, and the oxyhydroxide of metal, carbonate or oxide compound are preferred.Wherein, Na0H, KOH, LiOH are preferred, and NaOH is most preferred, has superperformance.In addition, do not use two valencys or the compound of high-valency metal more, because do not recognize the influence of adding.
In the carboxyl in ethene-copolymers of unsaturated carboxylic acids is 1mol, and the amount of a divalent metal compound is in the scope of 0.02-0.4mol (2-40mol%).When the amount of metallic compound during less than 0.02mol, the stability of emulsion deficiency.On the other hand, when surpassing 0.4mol, the water absorbability of the resin layer that obtains (especially for alkaline solution) increases, and has lowered the resistance to tape peeling after solidity to corrosion and the oil removing, and this is not preferred.The lower limit of metallic compound amount is 0.03mol more preferably, more preferably 0.1mol, more preferably 0.5mol, more preferably 0.2mol of the upper limit of metallic compound amount simultaneously.
Use an above-mentioned amine and a divalent metal compound in the preferable range of quantity as mentioned above, they are used for the carboxyl of neutralization of ethylene-copolymers of unsaturated carboxylic acids with emulsification.Therefore, preferred total amount (dosis neutralisata) is excessive, because the viscosity of emulsion compositions sharply increases, cause sometimes solidifying, and excess base content has reduced solidity to corrosion, and has needed a large amount of evaporation energy.But also not preferred dosis neutralisata deficiency is because this has reduced emulsifying property.Therefore, the total amount of the amine of use and a divalent metal compound in the scope of 0.3-1.0mol, is 1mol in the carboxyl in ethene-unsaturated several acid copolymers preferably.
In the neutralization procedure (emulsifying step) of the ethene-copolymers of unsaturated carboxylic acids that utilizes amine and monovalent metallic ion, preferably approximately adds boiling point simultaneously and is lower than 100 ℃ amine and a divalent metal compound in multipolymer, or adds boiling point in advance and be lower than 100 ℃ amine.Although reason is unclear, when adding boiling point after a while when being lower than 100 ℃ amine, the effect that improves solidity to corrosion and resistance to tape peeling is insufficient sometimes.
In emulsion compositions, sneak into have can with the linking agent of two or more functional groups of carboxyl reaction.It is mixed for chemically crosslinked ethene-copolymers of unsaturated carboxylic acids to improve the intensity of layer.Solids content in emulsion compositions is 100 quality %, and the quantity of linking agent is 1-20 quality % (more preferably 5-10 quality %).When it during less than 1 quality %, insufficient by the cross-linking effect of chemical bonding, make it be difficult to provide the effect that improves solidity to corrosion and resistance to tape peeling.On the other hand, when mixing it when surpassing 20 quality %, the cross-linking density of resin layer excessively increases, and has increased hardness, and layer can not be out of shape when extruding and cause breaking, and therefore, but has reduced solidity to corrosion and screening characteristics, and this is not preferred.Preferably the quantity that changes linking agent according to the reasonable quantity of carboxyl in the multipolymer changes the quantity ratio of linking agent and ethene-unsaturated several acid copolymers.Usually, based on 100 mass parts multipolymers, linking agent is preferably 0.5-50 mass parts (more preferably 5-20 mass parts).
Can there be particular restriction with the linking agent of two or more functional groups of carboxyl reaction to having in the molecule, preferred example comprises, the linking agent that for example contains glycidyl, as polyglycidyl ether, as Sorbitol Powder polyglycidyl ether, (gathering) glycerine polyglycidyl ether, tetramethylolmethane polyglycidyl ether, TriMethylolPropane(TMP) polyglycidyl ether, neopentyl glycol diglycidyl ether and (gathering) ethylene glycol bisthioglycolate Synthesis of Oligo Ethylene Glycol and poly epihydric alcohol amine; With the linking agent that contains '-aziridino, difunctionality aziridine cpd for example, as 4,4 '-two (ethyliminum carbonylamino) ditane, N, N '-hexa-methylene-1,6-two (1-aziridine carboxylic acid amides), N, N '-ditan-4,4 '-two (1-aziridine carboxylic acid amides) and the two aziridine carboxylic acid amides of toluene; With three-or higher functional aziridine cpd, as three-1-'-aziridino phosphine oxide, three [1-(2-methyl) '-aziridino] phosphine oxide, TriMethylolPropane(TMP)-three (β-aziridine propionate), three-2,4,6-(1-'-aziridino)-1,3,5-triazine and tetramethyl-propane four '-aziridino propionic esters, or their derivative.Wherein, can use one or more linking agents.Especially, the linking agent that contains '-aziridino is preferred.Can use polyfunctional aziridine and simple function aziridine (ethylene imine etc.) simultaneously.
Can in emulsion compositions, mix and be converted into the silica dioxide granule that solids content quantity is 5-40 quality % (more preferably 20-30 quality %).But this is effectively to improving solidity to corrosion screening characteristics and flaw resistance, and also effective to solidity to corrosion and resistance to tape peeling after the raising oil removing.Under the situation of silica dioxide granule quantity not sufficient, effect is difficult to manifest.On the other hand, when excessive, the ratio of silica dioxide granule becomes too high, has destroyed film forming properties, and resin layer broken in drying step sometimes, and this may undesirably cause solidity to corrosion to reduce.In addition, silica dioxide granule works to improve the abrasive material of layer oilness, reduces frictional coefficient, and causes the wearing and tearing to mould in manufacturing processed, has shortened the life-span of mould.
For obtaining the maximum efficiency of silica dioxide granule, the mean particle size of preferred silica dioxide granule is in the scope of 1-200nm.Granularity at silica dioxide granule surpasses under the situation of 200nm, and it makes the surperficial roughen of resin layer, can not obtain fine and close resin layer, and in addition, silica dioxide granule has also reduced workability as abrasive material.When the granularity of silica dioxide granule hour, the solidity to corrosion of layer is improved.But, because when particle was extremely thin, above-mentioned effect was saturated, so the preferred 1nm of the lower limit of granularity.Under the situation of the solidity to corrosion particularly important after the oil removing, the mean particle size of silica dioxide granule is preferably in the scope of 4-20nm.This silica dioxide granule is commonly referred to colloidal silica, for example, can preferably use " XS ", " SS ", " 40 ", " N " and " UP " in " SNOWTEX " series (colloidal silica, Nissan Chemical Industry Co. produces).
The emulsion compositions preferred package content of wax of the present invention.To be converted into solids content be 0.5-20 quality % (0.5-10 quality % more preferably comprising, under the situation of wax more preferably 0.5-5 quality %), obtain oilness, flaw resistance, deep drawing quality, the press forging of resin layer or impact the impact that needs and resistant to mold wear and manufacturing processed in the anti-blackening at sliding surface place all be favourable.But, the quantity of preferred wax is inexcessive, because boundary or the boundary surface-treated layer and resin layer between of wax between the coating after resin layer and the coating can soften liquefaction or floating loose (bloom) and thickening, this has reduced solidity to corrosion and the resistance to tape peeling after the oil removing.
Wax is not had particular restriction, can use any known wax, as natural wax, for example Microcrystalline Wax and paraffin; Synthetic wax, for example polyethylene wax; With their mixture.Preferred selection softening temperature is those of 80-140 ℃.Most preferred wax is spherical polyethylene wax, and its mean particle size is 0.1-3 μ m (more preferably 0.3-1.0 μ m).This is because can significantly improve oilness, impact, resistant to mold wear and deep drawing quality.For spherical polyethylene wax, can use commerical prod, preferably include " W-100 ", " W-200 ", " W-300 ", " W-400 ", " W-500 ", " W-640 ", " W-700 " (Mitsui Chemical Co. production) and " ELEPON-20 " (Nikka Chemical Co. production) in for example " DIJET E-17 " (Goou Chemical Co. production), " KUE-1 ", " KUB-5 " and " KUE-8 " (Sanyo Kasei Industry Co. production), " CHEMIPEARL " series.
The emulsion compositions that uses among the present invention preferably comprises ethene-copolymers of unsaturated carboxylic acids, amine, a divalent metal compound and linking agent such as aziridine cpd as basal component, and also has optional silica dioxide granule and the wax that uses.Preferably in ethene-unsaturated several acid copolymers, adjust the quantity of aziridine cpd, silica dioxide granule and wax, make that resinous principle is 50 quality % or higher for the solids content of emulsion compositions.
Prepare emulsion compositions by following method: at first will for example be encased in the homogenizer equipment together with water medium as ethene-unsaturated several acid copolymers of basal component, choose wantonly at 70-250 ℃ and heat them down, add an amine and a divalent metal compound (add amine in advance or add amine substantially simultaneously and a divalent metal compound) with the form of the aqueous solution etc. aptly separately, under high shear stir them then.Can add silica dioxide granule, wax and linking agent in any stage, but preferably after adding linking agent, not heat, so that do not carry out crosslinking reaction and cause gel.
In emulsion compositions, can in the scope that does not hinder the object of the invention, suitably add diluting solvent, surface-protective agent, levelling agent, defoaming agents, permeate agent, emulsifying agent, film coalescence aid, tinting pigment, short stick, silane coupling agent and other resin.When other resin combination is used to form the top layer resin layer, also can use can with the various additives of emulsion compositions blended.
By using known drying means is that roller coat, spraying or showering (curtainflowcoating) are applying the above-mentioned emulsion composition and the dry resin layer that forms under heating on the one or both sides of metal sheet on metal sheet.The exsiccant temperature is preferably under the temperature that the crosslinking reaction between used linking agent and the carboxyl is carried out under heating.In addition,, preferably in 70-130 ℃ scope, carry out drying, because when keeping spherical form, the workability in the manufacturing step is favourable subsequently using under the situation of spherical polyethylene wax as lubricant.
The deposition of resin layer (thickness) is preferably 0.2-2.5g/m after drying
2Cross when thin when it, the uniform coating on the metal sheet is difficult, and is difficult to the well balanced layer character that obtains being scheduled to, but as workability, solidity to corrosion and screening characteristics.But the preferred deposition amount does not surpass 2.5g/m
2, destroyed because the ground connection conductivity is an electroconductibility, for example, be used under the situation of computer shell.In addition, the overburden amount of resin layer increases during compacting, and the layer under causing peeling off deposits and gathers on the mould, thereby causes the pressing mold trouble, and considers production cost, also wastes.The resin layer deposition more preferably be limited to 0.5g/m down
2, be limited to 2.0g/m on more preferably
2
Can obtain surface-treated steel plate galvanized by on surface reforming layer, forming above-mentioned resin layer as most preferred embodiment of the present invention.The surface-treated steel plate galvanized can use after procedure of processing, or using electrodeposition coating, powder coating or silk screen printing (keeping about 20-30 minute at about 130-160 ℃) back use, depends on purposes.
Do not comprise deleterious sexavalent chrome fully according to surface treatment steel plate galvanized of the present invention, and the resistance to tape peeling after resistance to tape peeling and the alkaline degreasing is good, resistance to tape peeling is at first recognized as problem by the inventor.In addition, under the situation of layer of selecting to obtain as top coat by the designated emulsion composition, the surface treatment steel plate galvanized that is formed with the good layer of various basic properties can be provided, but basic property is as screening characteristics, oilness, workability and solidity to corrosion, and the resistance to tape peeling of resistance to tape peeling and alkaline degreasing is significantly good.Therefore, this can be effectively usually as being applicable to for example surface treatment steel plate galvanized of automobile, household electrical appliance and material of construction.
Reference example is more specifically described the present invention, but the present invention never is limited to the following examples, but with scope above-mentioned and that hereinafter described main points are consistent in appropriate change the present invention, institute changes and all is included in the technical scope of the present invention.In the following embodiments, unless otherwise, " % " and " part " is meant " quality % " and " mass parts ".
Experimental example 1 (numbering 1 to 29)
Use that (parts number: SECC) surface is gone up the plated deposition amount and is 20g/m at the 0.8mm Plate Steel by electro-plating method
2Zinc, alkaline degreasing wash then and the exsiccant steel plate galvanized as raw material plate.Use and comprise phosphoric acid hydrogen aluminum water solution (Nippon Chemical Industry Co. produces, 50% solids content), colloidal silica (" SNOWTEX-O " separately; Nissan ChemicalIndustry Co. produces) and the surface treatment agent of the mixture of water.By changing the quantity of phosphoric acid hydrogen aluminum water solution, colloidal silica and water, and randomly add phosphoric acid and metallic aluminium come shown in table 1 and 2, to change Si, P and Al in the treatment agent separately concentration and change Si, P and Al content separately in the surface reforming layer.
Each steel plate galvanized after the oil removing was immersed in the surface treatment agent 2 seconds, pulls out then, remove redundant solution by squeezing roller after, washing is 5 seconds under the spray pressure of 50kPa, and at 40 ℃ of dry down surface reforming layers that form on zinc coating.Do not wash for the numbering in the table 2 29.
Respectively, by mixing and the epoxy type linking agent (" RICABOND AP355B " of stir solids content 5% (all being that solids content in the composition of formation top layer resin layer is 100% value here and hereinafter); Chuo Ri ka Industry Co. production), the silica dioxide granule (" SNOWTEX 40 " of the granularity 10-20nm of solids content 30%; Nissan ChemicalIndustry Co. produces) and the spherical polyethylene wax (" CHEMIPEARLW700 " of solids content 5%; Mitsui Chemical Co. produces) in polyolefin dispersion (" CHEMIPEARL (registered trademark) S100 ", Mitsui Chemical Co. produces), prepare the composition that is used to form the top layer resin layer.Be coated in coating composition on the surface reforming layer of each steel plate galvanized by rod, heat drying is 1 minute under 90 ℃ plate temperature, and obtaining being formed with deposition is 1g/m
2The surface treatment steel plate galvanized of top layer resin layer.
For each specimen sample that obtains like this, carry out evaluation test, comprise the amount (mg/m of Si, P and Al in the concentration (%), surface reforming layer of Si in the surface processing solution, P and Al
2), total deposition (mg/m of surface reforming layer
2) and resistance to tape peeling and alkaline degreasing after resistance to tape peeling, the results are shown in table 1.
[evaluation method]
(1) quantity of Si, P and Al
Respectively by Si, P and Al concentration separately in ICP emmission spectrum device (Seiko Advance Co. manufacturing) the surface measurements treatment soln, by fluorescent X-ray device (trade mark: " MIF-2100 "; Shimazu Seisakusho manufacturing) Si, P and Al quantity (mg/m separately in the surface measurements modified layer
2).Total deposition (mg/m of surface reforming layer
2) be that basis is passed through the fluorescent X-ray spectrochemical analysis, and in modified layer, form SiO by supposition Si, P and Al
2, AlPO
4, Zn
3(PO
4)
2And Al
2O
3And the quantized result of the Si that calculates, P and Al and the value that obtains.
(2) resistance to tape peeling
On the surface of test sample, paste silk ribbon (#9510, Surion Tech produce) and in the atmosphere of 40 ℃ of x90%RH stored sample peel off silk ribbon after 24 hours and 48 hours, observe the ratio that remains the top coat area, according to the anti-separability of following standard evaluation:
Zero: remaining proportion 100%
Zero-zero: remaining proportion 95% or above but less than 100%
Zero: remaining proportion 90% or above but less than 95%
Δ: remaining proportion 70% or above but less than 90%
*: remaining proportion is less than 70%.
(3) resistance to tape peeling after the oil removing
After being immersed in test sample except that oil solution, wherein alkaline degreasing agent (" CL-N364S "; Nippon Parkerizing Co. production) being adjusted at 60 ℃ is down 20g/l, pull out sample, washing and dry, glass paper tape (Nichiban Co. production) is attached on the surface of sample, and after 24 hours and 48 hours, peel off, observe the remaining proportion of residue top coat, according to normality under those identical standard evaluations of resistance to tape peeling.
Table 1 has shown embodiments of the invention.In each embodiment, in the surface reforming layer Si, P and Al separately content and Si/P and P/Al all in suitable scope, each embodiment shows good resistance to tape peeling under drying regime He after the oil removing.Since in the table 2 in the numbering 19 P/Al therefore compare less than suitable scope with embodiments of the invention, some is poor a little on resistance to tape peeling after resistance to tape peeling and the oil removing for it.
Numbering 20 and 23 is for wherein Si, P and Al add-on partially or completely do not reach the embodiment of predetermined amount in the surface reforming layer, because Si, P and Al concentration are partially or completely not enough in the surface-modifying agent, so the resistance to tape peeling after resistance to tape peeling and the alkaline degreasing is poorer than in the embodiment of the invention those.
Numbering 24-28: because Si, P and Al concentration are partly or entirely excessive in the surface-modifying agent, therefore the deposition of Si, P and Al partially or completely surpasses predetermined amount in the surface reforming layer, so the resistance to tape peeling after resistance to tape peeling and the alkaline degreasing is poorer than in the embodiment of the invention those.
Numbering 29: owing to should not wash with water, P in the surface reforming layer and the deposition of Al surpass predetermined amount.Although resistance to tape peeling is favourable, the alkali resistance of surface reforming layer is variation owing to the excessive of P and Al, and the resistance to tape peeling after the alkaline degreasing is poor.
Experimental example 2 (numbering 30-48)
By not using dip-coating but spraying preparation surface reforming layer.That is to say that the every kind of surface treatment agent (preparation method identical with experimental example 1) that has composition as shown in table 3 in spraying under the 50kPa spray pressure was removed redundant solution by squeezing roller after 2 seconds.Then, under the spray pressure of 50kPa water further wash they 5 seconds, at 40 ℃ of down dry surface reforming layers that on zinc coating, form.Mode by identical with experimental example 1 except said process, obtains being formed with the surface-treated steel plate galvanized of top coat.Estimate each test sample that obtains like this by the mode identical, the results are shown in table 3 with experimental example 1.
Experimental example 3 (numbering 49-72)
Surface treatment agent as shown in table 4 is formed in the mixing solutions preparation of the aqueous solution by using phosphoric acid hydrogen aluminium, colloidal silica (above-mentioned " SNOWTEX-0 "), three kinds of polyacrylic acid and water.At first, by spraying (with experimental example 2 under the identical condition) surface treatment steel plate galvanized before at first obtaining forming top coat.Form top coat on them by the mode identical, form numbering 49-60 with embodiment 1.
Then, respectively, by adding 626 parts of water and 160 parts of ethylene-acrylic acid copolymer (vinylformic acid 20 quality %, melting index (MI) 300) in autoclave, the triethylamine of 40mol%, in carboxyl in the ethylene-acrylic acid copolymer is 1 mole of NaOH that adds 15mol%, stirs the emulsion that obtains ethylene-acrylic acid copolymer 150 ℃ of atmosphere high speeds with 5Pa.Then, by mixing and stirring solids content as linking agent be 5% linking agent that contains glycidyl (" EPICLON CR5L " of (and hereinafter, all be based on solids content in the emulsion compositions here be 100% value); (CR5L is abbreviation); " EPICLON " is registered trademark; Dainippon Ink Chemical Industry Co. produces) and solids content be 5% the linking agent that contains '-aziridino (4,4 '-two (ethyleneimino carbonylamino) ditan; " CHEMITITE DZ-22E "; (DZ-22E is abbreviation); " CHEMITITE " is registered trademark; Nippon Catalyst Co. production), solids content is that 30% granularity is the silica dioxide granule (" SNOWTEX 40 " of 10-20nm; Nissan Chemical Industry Co. produces) and solids content be that 5% mean particle size is that 1 μ m and softening temperature are that 120 ℃ spherical polyethylene wax prepares emulsion compositions.Be coated on the surface reforming layer that forms the surface treatment steel plate galvanized before the top coat by rod and apply emulsion compositions, heat drying is 1 minute under 90 ℃ plate temperature, and the formation deposition is 1g/m
2Top layer resin layer (numbering 61-72).
Estimate each test sample that obtains like this by the mode identical, the results are shown in table 4 and 5 with experimental example 1.In table, PA1 is that weight-average molecular weight (Mw) is the polyacrylic acid of 100000-200000, and PA2 is that Mw is the polyacrylic acid of 20000-30000, and PA3 is that Mw is 8000 polyacrylic acid.The specific absorption of resin is the value of measuring by FT-IR in the surface reforming layer, and analysis condition is as shown below.
[FT-IR analytical procedure]
Measuring method: high sensitive method for reflection
(75 ° of input angles, IR light as parallel polarized light by radiation)
Contrast material: the mirror of golden vapour deposition
Resolving power: 4cm
-1
Accumulative frequency: 500 times
Device: JIR-5500 type Fourier transform IR spectrophotometer, Nippon Denshi Co.
Make IR-RSC110 reflection measurement unit (variable-angle type)
IR-SEM100 sample board
From adding polyacrylic steel plate at 1496cm
-1-1776cm
-1The peak area at place deducts and does not add polyacrylic steel plate at 1496cm
-1-1776cm
-1The peak area at place determines that difference is as coming from polyacrylic specific absorption in the surface reforming layer.Fig. 1-Fig. 3 shown number 38 described in the table of measuring under these conditions 3, the FT-IR spectrum of numbering 52 described in the table 4 and sodium polyacrylate (standard specimen).Numbering 52 among Fig. 2 is for comprise the system of 0.50g/l PA1 in surface treatment agent, wherein at 1346cm
-1, 1421cm
-1, 1457cm
-1And 1592cm
-1The place observes absorption, does not observe and do not comprise in surface treatment agent in the spectrum of polyacrylic numbering 38.The peak is identical with the absorption of sodium polyacrylate shown in Figure 3.
Can find out that the system that adds organic resin is than all excellent aspect the resistance to tape peeling of conventional not adding type after resistance to tape peeling and alkaline degreasing.In addition, can find out that the embodiment that is formed with top coat shows the resistance to tape peeling of remarkable excellence and the resistance to tape peeling after the alkaline degreasing, wherein top coat comprises by specifying neutralization method (shown in the table 5) neutral emulsion compositions.
Industrial applicibility
Because with the surface treatment that comprises Si, the P of specified quantity and Al and optional organic resin The Zn-based plating layer of agent in galvanized steel plain sheet forms surface reforming layer, resistance to tape peeling and alkaline process Resistance to tape peeling excellence after the oil removing. In addition, obtained by the designated emulsion composition by selection Layer can provide the surface treatment galvanized steel of the layer that is formed with various function admirables as top coat Plate, but wherein various performances such as screening characteristics, lubricity, machinability and corrosion resistance and outstanding Deoiling step after the resistance to tape peeling performance. Manufacturing method according to the invention is suitable for producing anti-With the good surface treatment galvanized steel plain sheet of resistance to tape peeling behind the fissility especially alkali degreasing.
Claims (12)
1. surface-treated steel plate galvanized, this steel plate galvanized has in the Zn-based plating layer on the steel plate galvanized, at the surface reforming layer that forms on the described Zn-based plating layer, the top coat that forms on described surface reforming layer, and wherein surface reforming layer comprises that to be converted into Si be 1-30mg/m
2SiO
2, 0.5-15mg/m
2P and 0.4-10mg/m
2Al.
2. according to the surface-treated steel plate galvanized of claim 1, wherein the mass ratio of the Si that comprises in the surface reforming layer, P and Al content separately satisfies following relationship formula (1) and (2):
0.5≤Si/P≤20 (1)
0.7≤P/Al≤5 (2)。
3. according to the surface-treated steel plate galvanized of claim 1, wherein surface reforming layer also comprises organic resin.
4. according to the surface-treated steel plate galvanized of claim 3, wherein comprise organic resin and make that the specific absorption that comes from the organic resin structure when observing surface reforming layer under FT-IR is 0.1-15.
5. according to the surface-treated steel plate galvanized of claim 1, wherein the deposition of surface reforming layer is at 4.2-130mg/m
2Scope in.
6. according to the surface-treated steel plate galvanized of claim 1, wherein top coat is for from comprising the resin layer that ethene-copolymers of unsaturated carboxylic acids obtains as the emulsion compositions of main component, except ethene-copolymers of unsaturated carboxylic acids, it be 100 ℃ or lower and quantity in the carboxyl of ethene-copolymers of unsaturated carboxylic acids is 1 mole of amine that is equivalent to 0.2-0.8mol that emulsion compositions comprises boiling point, and quantity is 1 mole of divalent metal compound that is equivalent to 0.02-0.4mol in the carboxyl of ethene-copolymers of unsaturated carboxylic acids; Comprise also with emulsion compositions that to have two or more can be the linking agent of the 1-20 quality % of 100 quality % in emulsion condition solids content with the functional group and the quantity of carboxyl reaction.
7. SiO that contains that is used on steel plate galvanized forming surface reforming layer
2Bonderite, wherein solids concn is 0.01-14.5 quality %, the quantity of the Si that comprises in the treatment agent, P and Al and form mass ratio and meet the following conditions:
Si:0.002-4.5 quality %
P:0.0005-1.5 quality %
Al:0.0001-0.5 quality %
1.5≤Si/P≤60，4.5≤Si/Al≤230。
8. according to the surface treatment agent of claim 7, wherein surface treatment agent also comprises organic resin, and wherein organic resin is water miscible.
9. surface treatment agent according to Claim 8 wherein comprises the organic resin of counting 0.01-3g/l with solids content in the surface treatment agent.
10. a manufacturing is according to the method for the surface-treated steel plate galvanized of claim 1, this method comprises that the surface treatment agent with description in the claim 7 forms the surface treatment agent layer on the surface of steel plate galvanized, should wash with water and from the surface treatment agent layer, remove excessive P and/or Al, the dry surface reforming layer that forms.
11. according to the manufacture method of claim 10, wherein the surface treatment agent layer forms by spraying.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003106998 | 2003-04-10 | ||
| JP106998/2003 | 2003-04-10 | ||
| JP045095/2004 | 2004-02-20 |
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| CN100507075C true CN100507075C (en) | 2009-07-01 |
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| JP5478588B2 (en) * | 2011-11-18 | 2014-04-23 | 株式会社神戸製鋼所 | Surface-treated metal plate with excellent corrosion resistance and conductivity |
| CN106164335B (en) * | 2014-04-04 | 2018-12-04 | 日涂表面处理化工有限公司 | Metal conditioner, coating method and the coating steel of galvanized steel |
| CN111235576B (en) * | 2020-01-15 | 2020-12-25 | 浙江大学 | Method for constructing micro-nano porous organic acid pretreatment layer on metal surface and application |
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