CN1242436A - Conditioning liquid and conditioning process used in pretreatment for forming of phosphate layer on metallic surface - Google Patents
Conditioning liquid and conditioning process used in pretreatment for forming of phosphate layer on metallic surface Download PDFInfo
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- CN1242436A CN1242436A CN99110660A CN99110660A CN1242436A CN 1242436 A CN1242436 A CN 1242436A CN 99110660 A CN99110660 A CN 99110660A CN 99110660 A CN99110660 A CN 99110660A CN 1242436 A CN1242436 A CN 1242436A
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- phosphate
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- regulator solution
- phosphate layer
- metallic surface
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/78—Pretreatment of the material to be coated
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
- C23C22/08—Orthophosphates
Abstract
Novel conditioning liquid used in pretreatment for formation of phosphate layer, being suitable for efficiently produce finly crystalized phosphate layer, also being durable of its excellent properties are disclosed. The conditioning liquid of the invention contains phosphate particles of bivalent and or trivalent metal, also contains a accelerating component. As for the accelerating component, saccharides, phosphoric acid compounds, polymer of acetic acid vinyl and designated aqueous high molecular compounds are favorable. The size of the phosphate particles are preferable to be less than 5 mum. And the concentration of the accelerating component are preferable to ba 1 to 2000 ppm. Before a process of formation of phosphate layer, the metallic surface is made to contact with the conditioning solution. Cleaning effect is possible to give to the conditioning liquid.
Description
The present invention relates to a kind of treatment solution and surface modulation method that is used for surface modulation, form phosphate layer in order to the ground of chemical on the metallic surface, can be applicable to such as steel, steel plate galvanized, aluminium and magnesium alloy etc.,, the phosphate crystal in the phosphate layer is attenuated to promote and to quicken chemical reaction.
Recently, a kind of demand that forms fine and closely woven phosphate crystal in phosphate layer is arranged,, and reduce the friction of this metal under cold operation in order to the erosion resistance after the improvement coating.Therefore use the surface modulation method earlier before often forming phosphate layer,, and make the nucleus that is suitable for producing fine and closely woven phosphate crystal with the activated metal surface in chemical ground.Hereinafter illustration is commonly used to obtain the method for fine and closely woven phosphate crystal.The phosphoric acid salt series of strata produce according to following steps.(1) removes fatty oil (2) washing (multiple-step form) (3) surface modulation (4) chemical ground and form phosphate layer (5) washing (multiple-step form) (6) rinsing in pure water.
The surface modulation method is suitable for making phosphate crystal to become fine and closely woven.The chemically composited material of Shi Yonging is disclosed in the United States Patent (USP) No. 2874081, No. 2322349 and No. 2310239 traditionally, wherein shows a kind of regulator solution, contains titanium, pyrophosphate ion, former phosphate ion and sodium ion etc.This matrix material is called Ztel's salt (Jernstedt salt), and the aqueous solution of this matrix material contains titanium ion and titanium colloid.
When metal impregnation sprays in aforementioned regulator solution or with aforementioned regulator solution, this metallic surface absorption titanium colloid.Adsorbed titanium colloid will become nucleus in the process of chemical ground formation phosphate layer, promote chemical reaction, and produce fine and closely woven crystallization.At present, the surface modulation matrix material of all industrial application all uses Ztel's salt (Jernstedt salt).Yet the industrial application of Ztel's salt (Jernstedt salt) produces problem miscellaneous.
First problem is that this surface modulation solution is degraded with the process of work time.Apply when using surface modulation solution always, at making phosphate crystal become fine and closely woven immediately after this aqueous solution of preparation, this salt has shown suitable obvious effects.But after the preparation a few days, no matter, all lose this kind effect whether through using, and the chap because of the titanium colloid condense in the regulator solution of the phosphate crystal of gained.
Hereat, JP63-76883A has disclosed a kind of method, and this surface modulation liquid of a configuration part also adds new surface modulation liquid continuously, periodic measurement and make titanium colloidal mean diameter keep enough little values.Though this kind method can be controlled this surface modulation liquid quantitatively, this part surface regulator solution need be handled to keep this kind effect.Therefore, this method need dispose a large amount of these surface modulation liquid and have jumbo water configuration device.
Second problem has very big relation for the effect of this surface modulation liquid and life-span and quality in order to the water for preparing.Usually, use tap water to prepare this surface modulation liquid.But known tap water contains positively charged ion such as calcium, magnesium etc. usually.And cationic content is decided on the water source.In the case, the known titanium colloid does not precipitate to keep dispersion because of the electric repulsion of the electric charge in the negatively charged ion.Therefore, if tap water contains excessive cationic composition, then the titanium colloid can be neutralized by the cationic composition, and loses its repulsive force so that condense and precipitate.
Someone is set forth in the phosphoric acid salt of interpolation condensation in this surface modulation liquid such as pyrophosphate salt, with the cationic composition of blockading, and keeps titanium colloidal stability.But when adding excessive condensed phosphate in this surface modulation liquid, may produce inert coating because of the reaction of the metallic surface in this condensed phosphoric acid and this regulator solution, the process of formation phosphate layer has problems with making in the subsequent disposal on metal chemical.The place of containing excessive calcium or magnesium in tap water needs to use pure water to make this regulator solution, causes shortcoming economically.
The 3rd problem is temperature and the pH when applying.For example, the titanium colloid promptly condenses in the scope that is higher than 35 ℃ temperature and exceeds pH8.0～9.5, forfeiture surface modulation effect.Therefore, Chang Yong surface modulation liquid must use in the specified temp and the pH scope of close limit.Therefore, can't be as making as the single-liquid type this surface modulation liquid produce cleaning effect.
The miniaturization that the 4th problem is phosphate crystal is restricted.The miniaturization of phosphate crystal forms from the titanium colloid nucleus that is adsorbed on this metallic surface, helps the detailed-oriented of phosphate crystal.Therefore, the titanium colloid that adsorbs on the metallic surface the more can obtain the fine and closely woven phosphate crystal of healing.
In order to solve this problem, be easy to expect that suggestion increases the titanium colloidal number in the regulator solution.But density is higher, and the frequency of bump is higher each other in this regulator solution for the titanium colloid, causes condensing and sedimentation the more.The titanium colloidal upper limit of using is lower than 100ppm at present, can't use higher density titanium colloidal regulator solution.
JP56-156778A and JP57-23066A have disclosed and have a kind ofly depressed the soluble phosphatic suspension that will contain divalence or trivalent metal and spray method on this steel face in adding.But only depress when spraying this suspension just display effect in adding, so method can't be applied to the general control method that makes this metal impregnation or spray this regulator solution.
JP40-1095B2 has disclosed another kind of surface modulation method, steel plate galvanized be impregnated in the soluble phosphatic suspension of divalence or trivalent metal.But the application example of this method only is confined to steel plate galvanized, and needs to use at least up to the soluble phosphoric acid salt of the high-density of 30 grams per liters.
Illustrated as preamble, the method relevant with Ztel's salt (Jernstedt salt) presented so various problem.Yet, the method that can replace this Ztel's method (Jernstedtmethod) is not arranged at present yet.
The problem of the aforementioned common technology of purpose system's solution of the present invention provides a kind of regulator solution of novelty and the control method of novelty, and their promote and quicken chemical reaction, make phosphate crystal become thinner, and keep long stable.
People such as present inventor further investigate at solving foregoing problems, obtain a kind of surface modulation liquid and control method that can further improve the novelty of phosphate layer quality at last.
Promptly, the present invention is (1): a kind of regulator solution for the pre-treatment use that forms phosphate layer on the metallic surface, it is characterized by it and contain the phosphate particle of one or more divalence or trivalent metal, and contain one or more acceleration composition, be selected from single candy, polysaccharide and derivative thereof.
And, the present invention is (2): a kind of regulator solution for the pre-treatment use that forms phosphate layer on the metallic surface, it is characterized by the phosphate particle that it contains one or more divalence or trivalent metal, and contain one or more and quicken composition, be selected from orthophosphoric acid salt, polyphosphate and organic phospho acid compound.
And, the present invention is (3): a kind of regulator solution for the pre-treatment use that forms phosphate layer on the metallic surface, it is characterized by the phosphate particle that it contains one or more divalence or trivalent metal, and contain one or more water soluble polymer compound and quicken composition, be selected from polymkeric substance, its derivative and vinyl acetate base and other monomeric multipolymers of vinyl acetate base.
And, the present invention is (4): a kind of regulator solution for the pre-treatment use that forms phosphate layer on the metallic surface, it is characterized by the phosphate particle that it contains one or more divalence or trivalent metal, and contain one or more and quicken composition, be selected from by the following monomer i of polymerization) and the following monomer that is lower than 50 weight the % ii) polymkeric substance or the multipolymer of gained.Monomer i) monomer shown in the following formula (1) or be selected from α-, β-unsaturated carbon acid mono.Monomer ii) can with aforementioned monomer i) monomer of copolymerization.
Wherein, R
1: H or CH
3, R
2: the hydroxyalkyl of the alkyl of H or C1～5 or C1～5.
In aforementioned (1)～(4), phosphate particle should advantageously contain diameter less than 5 microns particle, and preferred total concn is 0.001～30 grams per liter, and divalence or trivalent metal are preferably the metal of at least a Zn of being selected from, Fe, Mn, Ni, Co, Ca and Al.And the total concn of quickening composition is preferably 1～2000ppm.
In addition, regulator solution preferably also contains other alkali metal salt or ammonium salt or its mixture.These alkali metal salts or ammonium salts are preferably orthophosphoric acid salt, metaphosphate, ortho-silicate, metasilicate, carbonate, supercarbonate, nitrate, nitrite, vitriol, borate and organic acid salt, preferable total concn 0.5～20 grams per liter.
Control method of the present invention is before forming phosphate layer, the metallic surface to be contacted with aforementioned regulator solution.
Because regulator solution of the present invention has under high pH scope and high temperature than the high stability of titanium colloid in the common technology.Hereat, regulator solution of the present invention can contain alkaline constituents and one or more than a kind of additive in addition, is selected from nonionic surfactant and anionic surfactant.This kind regulator solution also can have another effect on clean metal surface.The metal of handling through this regulator solution has clean Surface, also has the character that is suitable for forming phosphate layer.
Illustrated as preamble, in common method, before chemical ground forms phosphate layer, need carry out (1) earlier and remove fatty oil, three steps such as (2) washing and (3) surface modulation.The application of the invention has the regulator solution of cleaning (degreasing) effect and surface modulation effect concurrently, and this three step can be simplified to one step, in conjunction with the method for degreasing and surface modulation, as hereinafter as described in (1).That is, can reduce by two steps.
Regulator solution of the present invention can provide the surface that is suitable for forming in the wideer pH scope of pH scope commonly used phosphate layer effectively.Hereat, the present invention can add an alkali metal salt in addition in this regulator solution, and the present invention can obtain having concurrently the regulator solution of cleaning and surface modulation effect.(1) method (2) the chemical ground in conjunction with degreasing and surface modulation forms phosphate layer (3) washing (multiple-step form) (4) rinsing in pure water
The phosphate particle of divalence or trivalent metal and acceleration composition are neccessary composition of the present invention.As mentioned before, purpose of the present invention is that a kind of surface modulation liquid is provided, and it activated this metallic surface before forming phosphate layer, and produced the employed nucleus of phosphorus supply hydrochlorate crystalline deposit.People such as present inventor find, phosphate particle with the divalence of preferable diameter or trivalent metal is when preferable content, be adsorbed in and await helping to produce the nucleus that the crystallization of phosphorus supply silicate layer is used, and quickening the formation of phosphate layer with on the metallic surface of containing the aqueous solution processing of quickening composition.
The phosphate particle of divalence of the present invention or trivalent metal is a solid and soluble.Yet, chemically, they be with in order to form the similar composition of chemical substance of phosphate layer, also chemically be similar to formed phosphate layer.They continue in the dipping bath even the part of this regulator solution is inserted the solution that is equipped with in order to form phosphate layer afterwards for not having negative impact in order to the solution that forms phosphate layer, also can not have a negative impact for this phosphate layer.The phosphate particle of divalence of the present invention or trivalent metal has for example following.Zn
3(PO
4)
2, Zn
2Fe (PO
4)
2, Zn
2Ni (PO
4)
2, Ni
3(PO
4)
2, Zn
2Mn (PO
4)
2, Mn
3(PO
4)
2, Mn
2Fe (PO
4)
2, Ca
3(PO
4)
2, Zn
2Ca (PO
4)
2, FePO
4, AlPO
4, CoPO
4, Co
3(PO
4)
2And the hydrate of this compounds.
The increase of sedimentary crystallization number diminished when phosphate layer crystalline particle diameter began with the work reaction.Because when adjacent crystallization contacted with each other, crystallization promptly stopped growing.And the crystallization number that reacts when beginning is higher, and the knot intergranular is apart from littler, so this metallic surface can be covered by less crystallization in the short period.Therefore, for the thinner phosphate crystal of precipitation in the short period of time, be preferable over and form the more nucleus of phosphate layer elder generation's manufacturing before.
With regard to the viewpoint in stably being scattered in this aqueous solution, the phosphatic particle diameter of divalence of the present invention or trivalent metal is preferably less than 5 microns.Even may contain diameter in the regulator solution of the present invention greater than 5 microns the divalence or the phosphoric acid salt of trivalent metal, but when this liquid also contain capacity less than 5 microns phosphate particle the time, do not destroy effect of the present invention.
The phosphate particle of divalence of the present invention or trivalent metal itself also has the sedimentary effect of promotion.Promptly, the phosphate particle of this divalence or trivalent metal can be adsorbed on this metallic surface in regulate process, and wherein some itself is dissolvable in water in the phosphate layer formation bath of subsequent step, near the metallic surface, provide phosphate component, and significantly promote the precipitation of phosphate layer this phosphate layer.
Ideally, divalence or trivalent metal phosphate particle total amount are between 0.001～30 grams per liter.When the phosphate particle total amount of divalence or trivalent metal is lower than 0.001 grams per liter, the phosphate particle amount that is adsorbed in divalence on the metallic surface or trivalent metal reduces, and can't promote the precipitation of phosphate crystal, and more a spot of particle also can't promote this chemical reaction.
When the phosphate particle amount of divalence or trivalent metal is higher than 30 grams per liters, only produce disadvantageous cost factor, and can't obtain further to promote again the effect of phosphatic formation.
The acceleration composition that regulator solution of the present invention comprises hereinafter will be described.
As mentioned before, in common technology, the soluble phosphoric acid salt of divalence or trivalent metal is depressed injection and is used for surface modulation in adding.In add the reason of depressing injection for by make this this metallic surface of soluble phosphoric acid salt hard collision or as spray as the tup and cut this metallic surface, can make it reaction.And for obtain the surface modulation effect with common method, the soluble phosphatic density of divalence or trivalent metal needs to increase to heavens.
It has been observed by the present inventors that when acceleration composition of the present invention exists,, still can obtain the surface modulation effect even in more low-density divalence or trivalent metal phosphate particle and do not use and it is sprayed under the situation of the physical force of metallic surface.Therefore, in the present invention, it is promptly enough that this metallic surface is contacted with this regulator solution.
The present invention quickens the dispersion stabilization that composition (being designated hereinafter simply as promotor) can improve the phosphate particle of divalence or trivalent metal, and promotes the absorption of phosphate particle on this metallic surface of divalent metal or trivalent metal.This promotor is adsorbed on the surface of each phosphate particle of divalence or trivalent metal, by giving the collision each other that phosphate particle electrical charge rejection power and solid stopping effect destroy the phosphate particle of divalence or trivalent metal, and prevent that phosphate particle from condensing and sedimentation.And promotor itself has the ability that is adsorbed in the metallic surface, and promotes phosphate particle to be adsorbed in the metallic surface by being adsorbed in the phosphate particle surface.Only, this metal can reach regulating effect by being contacted with this regulator solution.
Accelerator level is preferably 1～2000ppm.If be lower than 1ppm, then surface modulation liquid can't reach the surface modulation effect.If be higher than 2000ppm, then can't further improve its effect, the metallic surface is covered by promotor and this phosphate particle may become the danger that is difficult to be adsorbed in this metallic surface and produce.
In regulator solution of the present invention (1), should contain the promotor that is selected from single candy, polysaccharide and derivative thereof.The basic candy composition of single candy, polysaccharide and derivative thereof can be selected from following material: fructose, tagatose, psicose, husky uncle's sugar (sulbose), erythrulose, trehalose, ribose, pectinose, wood sugar, lichen sugar (lichetose), allose, altrose, glucose, seminose, gulose, idose, semi-lactosi, talose etc.
Therefore, if use single candy, but the basic candy base of application of aforementioned then.If desire is used polysaccharide, then use homopolysaccharide (homo-polysaccharide) or different polysaccharide (hetero-polysaccharide).Also can use its derivative, such as using substituted radical such as NO
2, CH
3, C
2H
4OH, CH
2CH (OH) CH
3, CH
2COOH etc. make the hydroxyl of this basic candy base carry out etherificate and single candy of making, or contain same candy (homo-saccharide) and the different candy (hetero-saccharide) that uses aforementioned group to replace single candy of gained.Also can use the combination of single candy, polysaccharide and derivative thereof.
The candy base also can be divided into single candy, few candy and polysaccharide according to its hydrolysis.In the present invention, they are divided into and can produce more than the polysaccharide of two single candys and further single candy of hydrolysis via hydrolysis.
Because the present invention and biochemical reaction are irrelevant, so the three-dimensional structure of its effect and basic single candy composition or opticity are irrelevant, and any combination of D-list candy, L-list candy and optically-active (+,-) all can be used.And, water-soluble in order to improve, can use the sodium salt and the ammonium salt of this list candy, polysaccharide and derivative thereof without a doubt.And, if relate to the problem of dissolving difficulty, then can be dissolved in the organic solvent earlier.
In regulator solution of the present invention (2), should contain one or quicken composition more than one, be selected from former phosphoric acid, Tripyrophosphoric acid or organic phospho acid.With regard to Tripyrophosphoric acid, can use tetra-sodium, triphosphoric acid, three metaphosphoric acids, four metaphosphoric acids, hexa metaphosphoric acid and sodium salt and ammonium salt.With regard to organic phospho acid, can use amido trimethylene phosphonic, 1-hydroxy ethylene-1,1-di 2 ethylhexyl phosphonic acid, ethylenediamine tetramethylene phosphonic acid, diethylenetriamine pentamethylenophosphonic acid(DTPP) and sodium salt thereof.Can be without a doubt indivedual or be used in combination this former phosphoric acid, Tripyrophosphoric acid and organic phospho acid.
In regulator solution of the present invention (3), should contain one or more than a kind of acceleration composition, be selected from the waterborne polymeric of vinyl acetate base and derivative thereof and vinyl acetate base with can with the monomeric multipolymer of vinyl acetate base copolymerization.With regard to the polymkeric substance of vinyl acetate base and derivative thereof, can use the vinyl acetate base polymkeric substance soap class form polyvinyl alcohol, by use vinyl cyanide with the cyanoethylation-polyvinyl alcohol of polyvinyl alcohol cyanoethylation gained, by use formalin make the Polyvinyl acetal gained formolation-polyvinyl alcohol, make the amido ethyl formateization-polyvinyl alcohol of polyvinyl alcohol by using urea, and by importing the water-based giant molecule compound of carboxyl, sulfuryl, amide group gained to the polyvinyl alcohol through amido ethyl formate gained.With regard to regard to the monomer of vinyl acetate base copolymerization, can use vinylformic acid, Ba Dousuan, MALEIC ANHYDRIDE etc.
The polymkeric substance of aforementioned vinyl acetate base or derivatives thereof or vinyl acetate base with can then bring into play effectiveness of the present invention fully with the monomeric multipolymer of vinyl acetate base copolymerization if having water-based.This effectiveness is not influenced by the polymerization degree or functional group's importing degree, and this monomer or multipolymer are can be without a doubt indivedual or be used in combination.
In regulator solution of the present invention (4), should contain one or, be selected from by the following monomer i of polymerization more than a kind of promotion composition) and be lower than 50% following the monomer ii) polymkeric substance or the multipolymer of gained.Monomer i): the monomer shown in the following formula (1) or be selected from α-, the monomer of β-unsaturated carbon acid mono.Monomer is ii): can with aforementioned monomer i) monomer of copolymerization.
In the formula, R
1: H or CH
3, R
2: H or have the alkyl of C1～5 or have the hydroxyalkyl of C1～5.
With regard to the monomer shown in the formula (1), can use methyl acrylate, ethyl propenoate, propyl acrylate, butyl acrylate, vinylformic acid pentyl ester, methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, butyl methacrylate, methacrylic acid pentyl ester, vinylformic acid hydroxyl methyl esters, Hydroxyethyl acrylate, Propylene glycol monoacrylate, vinylformic acid hydroxy butyl ester, vinylformic acid hydroxy pentane ester, hydroxy methyl methacrylate, hydroxyethyl methylacrylate, Rocryl 410, methacrylic acid hydroxy butyl ester, methacrylic acid hydroxy pentane ester.
And, with regard to α-, β-unsaturated carbon acid mono can use vinylformic acid, methacrylic acid, maleic acid.With regard to monomer ii) with regard to, can use vinyl acetate base, vinylbenzene, ethylene chloride, vinyl sulfonic acid.Can use without a doubt by polymerization wherein a monomer gained polymkeric substance, and by the multipolymer of several monomer gained wherein of polymerization simultaneously.
Regulator solution of the present invention can contain the combination of alkali metal salts or ammonium salt or this two salt.With regard to an alkali metal salt and ammonium salt, can use orthophosphoric acid salt, metaphosphate, ortho-silicate, metasilicate, carbonate, supercarbonate, nitrate, nitrite, vitriol, borate, and organic acid salt.Also can be used in combination salt without a doubt more than two kinds.
Be used for an alkali metal salt of the present invention and ammonium salt and can be used as alkaline constituents, can have identical effect with the contained person of industrial cleaners.They can make this regulator solution have water softening effect and degreasing effect, and help to improve the liquid stabilising of regulator solution, and give the sanitising agent effect.
Ideally, the amount of alkali metal salts or ammonium salt is 0.5～20 grams per liter.When being lower than 0.5 grams per liter, water softening effect and cleaning effect deficiency, then uneconomical when being higher than 20 grams per liters.
Different with liquid commonly used, regulator solution of the present invention can keep effect down in many environment.That is, regulator solution of the present invention compares with the regulator solution of using always, has the following advantages: (1) permanent stability height.(2) even importing contains high density Ca, the hard water of Mg does not still reduce this effect.(3) can under high temperature, apply.(4) can add an alkali metal salt miscellaneous.(5) tool stability in wide pH scope.
Regulator solution commonly used can reduce its character because of adding sanitising agent, is difficult to need simultaneously to be applied to the method for cleaning effect and regulating effect.In the present invention, can add sanitising agent such as an alkali metal salt and ammonium salt without a doubt.Can in regulator solution of the present invention, add other alkaline constituentses without a doubt in addition such as mineral alkali component, organic bases component and tensio-active agent.And, in the present invention, in this liquid, can add the phosphoric acid salt of sequestrant and condensation, make an addition to the effect of the cationic composition in the liquid with elimination.
The inventive method only need make this metallic surface contact with this adjusting liquid, and the duration of contact or the temperature of regulator solution be there is no certain restriction.And regulator solution of the present invention can be applicable to all types of metals such as steel, galvanized steel plate, aluminum or aluminum alloy and magnesium or magnesium alloy.
With regard to the phosphate layer formation method of being carried out after the present invention regulates, can use the method for any kind, comprise dipping, sprinkling, electrolysis etc.And, with regard to phosphate layer, can provide phosphoric acid salt such as zinc phosphate, trimagnesium phosphate or the calcium phosphate-zinc of any kind without a doubt.
Embodiment and Comparative Examples
Hereinafter will illustrate in greater detail the present invention by embodiment and Comparative Examples.In these embodiments, with the example of zinc phosphate layer as phosphate layer, yet the present invention also can be applicable to the phosphate layer of other types.[test piece]
SPC:(cold-rolled steel sheet: JIS-G-3141)
The steel plate of EG:(two sides electro-galvanizing: zinc-plated amount 20 gram/rice
2)
The GA:(steel plate, two sides hot dipping zinc coating: zinc-plated amount 45 gram/rice
2)
The steel plate of Zn-Ni:(two sides electronickelling-zinc alloy: plating amount 20 gram/rice
2)
Al:(aluminium sheet: JIS-5052)
MP:(magnesium alloy plate: JIS-H-4201).[processing of test piece]
Alkali degreasing uses FINE CLEANER 14460 (trade marks of Nihon Parkerizing Co.Ltd) to carry out, and is diluted to 2% with tap water, is sprayed under 42 ℃ and goes through 120 seconds on the sample.
Surface modulation liquid uses different types of solution.And sample impregnated in the solution.
The formation of phosphate layer uses PALBOND L 3020 (trade marks of Nihon ParkerizingCo.Ltd) to carry out, and is diluted to 4.8% with tap water.Sample flooded 120 seconds down in 42 ℃.
Washing reaches with rinsed with deionized water: carried out in 30 seconds by spraying under room temperature.[assessment of phosphate layer]
At following project evaluation phosphate layer.Promptly measure outward appearance, thin layer weight (C.W), thin layer grain size (C.S) and P-ratio.
Outward appearance---◎: good and evenly, zero: part is inhomogeneous, △: inhomogeneous and some thin area arranged, *: many thin areas are arranged, * *; No phosphate layer
C.W. (gram/rice
2): phosphate layer weight---W1 (gram): the sample weight after the phosphate layer of formation, W2 (gram): divest phosphate layer sample weight afterwards.C.W. (gram/rice
2)=(W1-W2)/(surface-area rice
2).
If steel plate, then divesting by this sample be impregnated in the chromic acid solution of phosphate layer undertaken; If steel plate galvanized then impregnated in this sample in the stripping composition that contains ammonium dichromate and ammonia.If aluminium and magnesium plate, then the P content in the zinc phosphate layer passes through the fluorescent X-ray measuring, and C.W. is based on aforementioned P cubage.
C.S (micron): the grain size of phosphate layer---on 1500 times of magnified images, assess grain size by scanning electronic microscope (SEM) gained.
P-ratio (%)---this experimental value only carries out on the SPC steel plate.According to P (the X-gamma intensity of tertiary iron phosphate hydrochlorate) and H (the X-gamma intensity of hopeite), obtain the P-ratio by following formula.
P-ratio=P/ (P+H)
Table 1 is listed the composition of the employed regulator solution of embodiment of claim 1.Table 2 is listed the employed regulator solution of Comparative Examples.Table 1 and 2 employed single candys, polysaccharide and the system commercially available prod of deriving.In the substituted radical, following chemical formula illustration is as the glucose of the single candy of basic structure.
If glucose, then position R
1, R
2And R
3On hydroxyl can be by etherificate.In embodiment, change substituted radical and substitution value (the basic candy structure of per unit is by the number of the hydroxyl that substituted radical replaced) with observing effect.Single candy of low water solubility, polysaccharide and derivative use sodium salt.The endurance test of prepared regulator solution (place test) keeps carrying out after 10 days under room temperature for making regulator solution.[embodiment 1]
The solution of zinc sulfate of 100 milliliter of 1 mol and 100 milliliter of 1 mol 1-sodium hydrogen phosphate solution alternately make an addition under 50 ℃ in 1 liter of 0.5 mol ferrous sulfate (II) solution, to produce sediment.The solution that contains sediment kept 1 hour so that the sediment maturation rinsing 10 times of tilting afterwards down in 90 ℃.After the filtration and the universe are dry, find that by the X-ray diffraction analysis this sediment is phosphoric acid phyllite (Zn
2Fe (POO
4)
24H
2O), part contains tertiary iron phosphate.In 1 kilogram of phosphoric acid phyllite, add 50 grams by with the listed 10 prepared weight % solution of single candy, polysaccharide and derivative of Virahol and water dilution table 1, in ball mill, use 0.5 mm dia zirconium dioxide bead to grind about 1 hour.After the grinding, use tap water that the phosphoric acid phyllite density in the suspension is transferred to 1 grams per liter and prepares the employed regulator solution of this embodiment.Measure with laser diffraction/diffusion size distribution analyser (LA-920:Horiba Seisakusho manufacturing), the median size that is suspended in this liquid is 0.5 millimeter.[embodiment 2]
The solution of zinc sulfate of 100 milliliter of 1 mol and 100 milliliter of 1 mol 1-sodium hydrogen phosphate solution alternately make an addition under 50 ℃ in 1 liter of 0.5 mol ferrous sulfate (II) solution, to produce sediment.The solution that contains sediment kept 1 hour so that the sediment maturation rinsing 10 times of tilting afterwards down in 90 ℃.After the filtration and the universe are dry, find that by the X-ray diffraction analysis this sediment is phosphoric acid phyllite (Zn
2Fe (PO
4)
24H
2O), part contains tertiary iron phosphate.In 1 kilogram of 10 weight % solution prepared, add 100 these phosphoric acid phyllites of gram, in ball mill, use 0.5 mm dia zirconium dioxide bead to grind about 1 hour by single candy, polysaccharide and the derivative listed with Virahol and water dilution table 1.After the grinding, use tap water that the phosphoric acid phyllite density in the suspension is transferred to 1 grams per liter and prepares the employed regulator solution of this embodiment.Measure with aforementioned laser diffraction/diffusion size distribution analyser, the median size that is suspended in this liquid is 0.5 micron.[embodiment 3]
The solution of zinc sulfate of 100 milliliter of 1 mol and 100 milliliter of 1 mol 1-sodium hydrogen phosphate solution alternately make an addition under 50 ℃ in 1 liter of 0.5 mol ferrous sulfate (II) solution, to produce sediment.The solution that contains sediment kept 1 hour so that the sediment maturation rinsing 10 times of tilting afterwards down in 90 ℃.After the filtration and the universe are dry, find that by the X-ray diffraction analysis this sediment is phosphoric acid phyllite (Zn
2Fe (PO
4)
24H
2O), part contains tertiary iron phosphate.In 1 kilogram of this phosphoric acid phyllite, add 100 grams by with the listed 10 prepared weight % solution of single candy, polysaccharide and derivative of water dilution table 1, in ball mill, use 0.5 mm dia zirconium dioxide bead to grind about 1 hour.After the grinding, use tap water that the phosphoric acid phyllite density in the suspension is transferred to 1 grams per liter and prepares the employed regulator solution of this embodiment.Measure with aforementioned laser diffraction/diffusion size distribution analyser, the median size that is suspended in this liquid is 0.5 micron.In addition, add 0.5 grams per liter Sodium Nitrite reagent, obtain the regulator solution of desiring to apply with as alkali salt.[embodiment 4]
The solution of zinc sulfate of 100 milliliter of 1 mol and 100 milliliter of 1 mol 1-sodium hydrogen phosphate solution alternately make an addition under 50 ℃ in 1 liter of 0.5 mol ferrous sulfate (II) solution, to produce sediment.The solution that contains sediment kept 1 hour so that the sediment maturation rinsing 10 times of tilting afterwards down in 90 ℃.After the filtration and the universe are dry, find that by the X-ray diffraction analysis this sediment is phosphoric acid phyllite (Zn
2Fe (PO
4)
24H
2O), part contains tertiary iron phosphate.In 1 kilogram of 10 weight % solution prepared, add 50 these phosphoric acid phyllites of gram, in ball mill, use 0.5 mm dia zirconium dioxide bead to grind about 1 hour by single candy, polysaccharide and the derivative listed with water dilution table 1.After the grinding, use tap water that the phosphoric acid phyllite density in the suspension is transferred to 1 grams per liter and prepares the employed regulator solution of this embodiment.Measure with aforementioned laser diffraction/diffusion size distribution analyser, the median size that is suspended in this liquid is 0.5 micron.In addition, add 0.5 grams per liter sal epsom, 7 hydrate reagent, obtain the regulator solution of desiring to apply with as alkali salt.[embodiment 5]
The solution of zinc sulfate of 100 milliliter of 1 mol and 100 milliliter of 1 mol 1-sodium hydrogen phosphate solution alternately make an addition under 50 ℃ in 1 liter of 0.5 mol ferrous sulfate (II) solution, to produce sediment.The solution that contains sediment kept 1 hour so that the sediment maturation rinsing 10 times of tilting afterwards down in 90 ℃.After the filtration and the universe are dry, find that by the X-ray diffraction analysis this sediment is phosphoric acid phyllite (Zn
2Fe (PO
4)
24H
2O), part contains tertiary iron phosphate.In 1 kilogram of 10 weight % solution prepared, add 50 these phosphoric acid phyllites of gram, in ball mill, use 0.5 mm dia zirconium dioxide bead to grind about 1 hour by single candy, polysaccharide and the derivative listed with water dilution table 1.After the grinding, use tap water that the phosphoric acid phyllite density in the suspension is transferred to 1 grams per liter and prepares the employed regulator solution of this embodiment.Measure with aforementioned laser diffraction/diffusion size distribution analyser, the median size that is suspended in this liquid is 0.5 micron.[embodiment 6]
The solution of zinc sulfate of 100 milliliter of 1 mol and 100 milliliter of 1 mol 1-sodium hydrogen phosphate solution alternately make an addition under 50 ℃ in 1 liter of 0.5 mol ferrous sulfate (II) solution, to produce sediment.The solution that contains sediment kept 1 hour so that the sediment maturation rinsing 10 times of tilting afterwards down in 90 ℃.After the filtration and the universe are dry, find that by the X-ray diffraction analysis this sediment is phosphoric acid phyllite (Zn
2Fe (PO
4)
24H
2O), part contains tertiary iron phosphate.In 1 kilogram of 10 weight % solution prepared, add 1 kilogram of this phosphoric acid phyllite, in ball mill, use 0.5 mm dia zirconium dioxide bead to grind about 1 hour by single candy, polysaccharide and the derivative listed with water dilution table 1.After the grinding, use tap water that the phosphoric acid phyllite density in the suspension is transferred to 1 grams per liter and prepares the employed regulator solution of this embodiment.Measure with aforementioned laser diffraction/diffusion size distribution analyser, the median size that is suspended in this liquid is 0.5 micron.[embodiment 7]
In 10 weight % solution of single candy, polysaccharide and the derivative of 1 kilogram of dilute with water, add 1 kilogram of Zn
3Fe (PO
4)
24H
2O uses 0.5 mm dia zirconium dioxide bead to grind in ball mill about 1 hour.After the grinding, use tap water with the Zn in the liquid
3Fe (PO
4)
24H
2O density transfers to 1 grams per liter and prepares this uses employed regulator solution.Measure with aforementioned laser diffraction/diffusion size distribution analyser, the median size that is suspended in this liquid is 0.6 micron.[embodiment 8]
In 1 kilogram of Zn
3Fe (PO
4)
24H
2In the O reagent, add the 10 weight % aqueous solution of listed single candy, polysaccharide and derivative gained of 10 gram dilute with water tables 1, in ball mill, use 10 mm dia zirconium dioxide beads to grind about 1 hour.After the grinding, use tap water with the Zn in the liquid
3Fe (PO
4)
24H
2O density transfers to 1 grams per liter.After the adjustment, the median size in the liquid is measured with aforementioned laser diffraction/diffusion size distribution analyser, and the median size that is suspended in this liquid is 1.2 microns.Add 5 grams per liter Starso reagent with as alkali, obtain the regulator solution of desiring to apply.[embodiment 9]
1 liter of 0.1 mol ca nitrate soln is in 50 ℃ of zinc nitrate solution and 200 milliliter of 1 mol 1-sodium hydrogen phosphates that add 200 milliliter of 1 mol down, to make it sedimentation.The solution that contains sediment kept 1 hour so that the sediment maturation rinsing 10 times of tilting afterwards down in 90 ℃.After the filtration and the universe are dry, find that by the X-ray diffraction analysis this sediment is scholzite (Zn
2Ca (PO
4)
22H
2O).In 1 kilogram of this scholzite, add 10 grams by with the listed 10 prepared weight % solution of single candy, polysaccharide and derivative of water dilution table 1, in ball mill, use 0.5 mm dia zirconium dioxide bead to grind about 1 hour.After the grinding, use tap water that the scholzite density in the suspension is transferred to 10 grams per liters.Measure with aforementioned laser diffraction/diffusion size distribution analyser, the median size that is suspended in this liquid is 0.4 micron.Add the yellow soda ash reagent of 1 grams per liter, obtain the regulator solution of desiring to apply.[embodiment 10]
1 liter of 0.1 mol ca nitrate soln is in 50 ℃ of zinc nitrate solution and 200 milliliter of 1 mol 1-sodium hydrogen phosphates that add 200 milliliter of 1 mol down, to make it sedimentation.The solution that contains sediment kept 1 hour so that the sediment maturation rinsing 10 times of tilting afterwards down in 90 ℃.After the filtration and the universe are dry, find that by the X-ray diffraction analysis this sediment is scholzite (Zn
2Ca (PO
4)
22H
2O).In 1 kilogram of this scholzite, add 10 grams by with the listed 10 prepared weight % aqueous solution of single candy, polysaccharide and derivative of water dilution table 1, in ball mill, use 0.5 mm dia zirconium dioxide bead to grind about 1 hour.After the grinding, use tap water that the scholzite density in the suspension is transferred to 5 grams per liters.Measure with aforementioned laser diffraction/diffusion size distribution analyser, the median size that is suspended in this liquid is 0.4 micron.In addition, the tertiary sodium phosphate reagent that adds 10 grams per liters is with as alkali, adds the polyoxyethylene of 2 grams per liters-ninth of the ten Heavenly Stems phenolic ether with as tensio-active agent, obtains the regulator solution of desiring to apply.In the case, under not degreasing, use to have the smeary test piece, clean simultaneously and regulate.[Comparative Examples 1]
Prepalene ZN (trade mark of Nihon Parkerizing Co.Ltd.), the aqueous solution, the employed regulator solution of common technology, under its standard conditions as regulator solution.[Comparative Examples 2]
In aforementioned Prepalene ZN solution, add the 7-Magnesium sulfate heptahydrate reagent of 0.5 grams per liter, adjusted liquid.[Comparative Examples 3]
The solution of zinc sulfate of 100 milliliter of 1 mol and 100 milliliter of 1 mol 1-sodium hydrogen phosphate solution alternately make an addition under 50 ℃ in 1 liter of 0.5 mol ferrous sulfate (II) solution, to produce sediment.The solution that contains sediment kept 1 hour so that the sediment maturation rinsing 10 times of tilting afterwards down in 90 ℃.After the filtration and the universe are dry, find that by the X-ray diffraction analysis this sediment is phosphoric acid phyllite (Zn
2Fe (PO
4)
24H
2O), part contains tertiary iron phosphate.This phosphoric acid phyllite uses 0.5 mm dia zirconium dioxide bead to grind in ball mill, when using aforementioned laser diffraction/diffusion size distribution analyser to measure, is suspended in median size in this liquid less than 0.5 micron.After the grinding, the density of this phosphoric acid phyllite transfers to 1 grams per liter with tap water, with adjusted liquid.[Comparative Examples 4]
The solution of zinc sulfate of 100 milliliter of 1 mol and 100 milliliter of 1 mol 1-sodium hydrogen phosphate solution alternately make an addition under 50 ℃ in 1 liter of 0.5 mol ferrous sulfate (II) solution, to produce sediment.The solution that contains sediment kept 1 hour so that the sediment maturation rinsing 10 times of tilting afterwards down in 90 ℃.After the filtration and the universe are dry, find that by the X-ray diffraction analysis this sediment is phosphoric acid phyllite (Zn
2Fe (PO
4)
24H
2O), part contains tertiary iron phosphate.This phosphoric acid phyllite ground in mortar about 2 minutes.After the grinding,,, abandon filtrate with 5 microns filter paper filterings with the tap water dilution.The sediment of gained is in dry 1 hour of 80 ℃ of following universes, adds 50 grams by 10 weight % solution with listed single candy, polysaccharide and derivative gained of water and isopropanol table 1 in the dry powder of 1 kilogram of institute's universe.With tap water the dry powder of this universe is transferred to density 1 grams per liter and prepares regulator solution.When using aforementioned laser diffraction/diffusion size distribution analyser to measure, the median size in the liquid is 6.5 microns.
Table 3 is listed the characteristic of the phosphate layer of embodiment gained, and phosphate layer all is zinc phosphate layer in all embodiment.
Table 4 is listed the characteristic of the phosphate layer of Comparative Examples gained, and phosphate layer also all is zinc phosphate layer in all Comparative Examples.
According to table 3 and 4 as can be known, listed as table 4, liquid commonly used has weak point, and the weather resistance of the regulator solution of the present invention that table 3 is listed is significantly improved.By Comparative Examples 3 and embodiment 1 and 2, understand to show the influence of single candy, polysaccharide and derivative thereof for surface modulation.The instant character of measuring in regulator solution preparation back of Comparative Examples 3 is poor than embodiment 1, but good than the liquid commonly used of Comparative Examples 1.
Yet, in Comparative Examples 3, the phosphatic pulverizing difficulty of divalence or trivalent metal, and, after this liquid prepares 10, the calcium phosphate precipitation of divalence or trivalent metal.This is because do not contain single candy, polysaccharide or derivatives thereof, so the phosphoric acid salt of this divalence or trivalent metal condenses once more.And, be difficult to make the close grain that is equivalent to embodiment.
Table 5 is listed the composition of the regulator solution of claim 2 of the present invention.In the present invention, the pH value of regulator solution is inessential.Yet when it was too sour, the danger that the solid phosphoric acid salt particle of divalence and trivalent metal is dissolved in the regulator solution improved.For fear of this kind situation, when its when acid too, by for example add sodium hydroxide with in and regulator solution be good.Endurance test is measured regulator solution keeps 10 under room temperature after.[embodiment 11]
The solution of zinc sulfate of 100 milliliter of 1 mol and 100 milliliter of 1 mol 1-sodium hydrogen phosphate solution alternately make an addition under 50 ℃ in 1 liter of 0.5 mol ferrous sulfate (II) solution, to produce sediment.The solution that contains sediment kept 1 hour so that the sediment maturation rinsing 10 times of tilting afterwards down in 90 ℃.After the filtration and the universe are dry, find that by the X-ray diffraction analysis this sediment is phosphoric acid phyllite (Zn
2Fe (PO
4)
24H
2O), part contains tertiary iron phosphate.In 1 kilogram of this phosphoric acid phyllite, add 10 weight % dilute aqueous solns of the listed phosphorus compound of 2 gram tables 5, in ball mill, use 0.5 mm dia zirconium dioxide bead to grind about 1 hour.After the grinding, use tap water that the phosphoric acid phyllite density in the suspension is transferred to 5 grams per liters and prepares the employed regulator solution of this embodiment.Measure with aforementioned laser diffraction/diffusion size distribution analyser, the median size that is suspended in this liquid is 0.5 micron.In addition, add 0.5 grams per liter sal epsom 7-hydrate reagent, obtain the regulator solution of desiring to apply with as alkali salt.[embodiment 12]
The solution of zinc sulfate of 100 milliliter of 1 mol and 100 milliliter of 1 mol 1-sodium hydrogen phosphate solution alternately make an addition under 50 ℃ in 1 liter of 0.5 mol ferrous sulfate (II) solution, to produce sediment.The solution that contains sediment kept 1 hour so that the sediment maturation rinsing 10 times of tilting afterwards down in 90 ℃.After the filtration and the universe are dry, find that by the X-ray diffraction analysis this sediment is phosphoric acid phyllite (Zn
2Fe (PO
4)
24H
2O), part contains tertiary iron phosphate.In 1 kilogram of this phosphoric acid phyllite, add 10 weight % dilute aqueous solns of the listed phosphorus compound of 1 kilogram of table 5, in ball mill, use 0.5 mm dia zirconium dioxide bead to grind about 1 hour.After the grinding, use tap water that the phosphoric acid phyllite density in the suspension is transferred to 1 grams per liter and prepares the employed regulator solution of this embodiment.Measure with aforementioned laser diffraction/diffusion size distribution analyser, the median size that is suspended in this liquid is 0.5 micron.In addition, add 1 grams per liter Starso reagent, obtain the regulator solution of desiring to apply as alkali salt.[embodiment 13]
The solution of zinc sulfate of 100 milliliter of 1 mol and 100 milliliter of 1 mol 1-sodium hydrogen phosphate solution alternately make an addition under 50 ℃ in 1 liter of 0.5 mol ferrous sulfate (II) solution, to produce sediment.The solution that contains sediment kept 1 hour so that the sediment maturation rinsing 10 times of tilting afterwards down in 90 ℃.After the filtration and the universe are dry, find that by the X-ray diffraction analysis this sediment is phosphoric acid phyllite (Zn
2Fe (PO
4)
24H
2O), part contains tertiary iron phosphate.In the 10 weight % aqueous solution of the listed phosphorus compound of 1 kilogram of table 5, add 200 these phosphoric acid phyllites of gram, in ball mill, use 10 mm dia zirconium dioxide beads to grind about 1 hour.After the grinding, use tap water that the phosphoric acid phyllite density in the suspension is transferred to 1 grams per liter and prepares the employed regulator solution of this embodiment.Measure with aforementioned laser diffraction/diffusion size distribution analyser, the median size that is suspended in this liquid is 1.7 microns.[embodiment 14]
In 1 kilogram of Zn
3Fe (PO
4)
24H
2In the O reagent, add the 10 weight % aqueous solution of the listed phosphorus compound of 100 gram tables 5, in ball mill, use 0.5 mm dia zirconium dioxide bead to grind about 1 hour.After the grinding, use tap water with the Zn in the liquid
3Fe (PO
4)
24H
2O density transfers to 5 grams per liters.After the adjustment, the median size in the liquid is measured with aforementioned laser diffraction/diffusion size distribution analyser, and the median size that is suspended in this liquid is 0.6 micron.Add 5 grams per liter yellow soda ash reagent as alkali, obtain the regulator solution of desiring to apply.[embodiment 15]
1 liter of 0.1 mol ca nitrate soln is in 50 ℃ of zinc nitrate solution and 200 milliliter of 1 mol 1-sodium hydrogen phosphates that add 200 milliliter of 1 mol down, to make it sedimentation.The solution that contains sediment kept 1 hour so that the sediment maturation rinsing 10 times of tilting afterwards down in 90 ℃.After the filtration and the universe are dry, find that by the X-ray diffraction analysis this sediment is scholzite (Zn
2Ca (PO
4)
22H
2O).In the 10 weight % aqueous solution of the listed phosphorus compound of 1 kilogram of table 5, add 1 kilogram of this scholzite, in ball mill, use 0.5 mm dia zirconium dioxide bead to grind about 1 hour.After the grinding, use tap water that the scholzite density in the suspension is transferred to 10 grams per liters.Measure with aforementioned laser diffraction/diffusion size distribution analyser, the median size that is suspended in this liquid is 0.5 micron.In addition, add the tertiary sodium phosphate reagent of 10 grams per liters as the polyoxyethylene of alkali and 2 grams per liters-ninth of the ten Heavenly Stems phenolic ether as tensio-active agent.In the case, under the situation of not degreasing, use test piece, to clean simultaneously and to regulate.[Comparative Examples 5]
The solution of zinc sulfate of 100 milliliter of 1 mol and 100 milliliter of 1 mol 1-sodium hydrogen phosphate solution alternately make an addition under 50 ℃ in 1 liter of 0.5 mol ferrous sulfate (II) solution, to produce sediment.The solution that contains sediment kept 1 hour so that the sediment maturation rinsing 10 times of tilting afterwards down in 90 ℃.After the filtration and the universe are dry, find that by the X-ray diffraction analysis this sediment is phosphoric acid phyllite (Zn
2Fe (PO
4)
24H
2O), part contains tertiary iron phosphate.This phosphoric acid phyllite ground in mortar about 2 minutes.After the grinding,,, abandon filtrate with 5 microns filter paper filterings with the tap water dilution.The sediment of gained adds 10 weight % solution of the listed phosphorus compound of 500 gram tables 2 in dry 1 hour of 80 ℃ of following universes in 100 these powder of gram.With tap water the dry powder of this universe is transferred to density 1 grams per liter and prepares regulator solution.Use aforementioned laser diffraction/diffusion size distribution analyser to measure, the median size in the liquid is 6.5 microns.
Table 6 is listed the characteristic of the formed phosphate layer of regulator solution that uses embodiment 11～15.Comparative Examples 5 formed phosphate layer characteristic series are shown in table 4.
By table 6 and 4 as can be known, to make be that the weather resistance of shortcoming of liquid commonly used is significantly improved to regulator solution of the present invention originally.The result of Comparative Examples 3 and embodiment 13 understands the influence that shows phosphorus compound.
Though the instant character of measuring in the regulator solution of Comparative Examples 3 preparation back is poor than embodiment 11, has the surface modulation effect good or suitable than the liquid commonly used of Comparative Examples 1.Yet in Comparative Examples 3, the phosphatic pulverizing of divalence or trivalent metal is difficulty very, and, after this liquid prepares 10, the calcium phosphate precipitation of divalence or trivalent metal.This is because do not contain the compound of former phosphoric acid, Tripyrophosphoric acid or organic phospho acid, so the phosphoric acid salt of this divalence or trivalent metal condenses once more.
Table 7 is listed the composition of the regulator solution of claim 3 of the present invention.In table 7 and table 2, the polymkeric substance or derivatives thereof of vinyl acetate base, represent with the aqueous high molecular compound simply with the aqueous high molecular compound of the multipolymer of vinyl acetate base polymeric monomer and vinyl acetate base.Polymkeric substance and derivative thereof use superoxide to make the polymerization of vinyl acetate base as initiator and make, and the functional group adds by soap or acetal chemical reaction.And, synthesize by vinyl acetate base and indivedual monomeric polymerization with the monomeric multipolymer of vinyl acetate base polymeric.
Endurance test is carried out in this regulator solution keeps 10 under room temperature after.[embodiment 16]
The solution of zinc sulfate of 100 milliliter of 1 mol and 100 milliliter of 1 mol 1-sodium hydrogen phosphate solution alternately make an addition under 50 ℃ in 1 liter of 0.5 mol ferrous sulfate (II) solution, to produce sediment.The solution that contains sediment kept 1 hour so that the sediment maturation rinsing 10 times of tilting afterwards down in 90 ℃.After the filtration and the universe are dry, find that by the X-ray diffraction analysis this sediment is phosphoric acid phyllite (Zn
2Fe (PO
4)
24H
2O), part contains tertiary iron phosphate.It is listed and through 10 weight % dilute aqueous solns of water-reducible aqueous high molecular compound, use 0.5 mm dia zirconium dioxide bead to grind in ball mill about 1 hour to add 2 gram tables 7 in 1 kilogram of this phosphoric acid phyllite.After the grinding, use tap water that the phosphoric acid phyllite density in the suspension is transferred to 5 grams per liters and prepares the employed regulator solution of this embodiment.Measure with aforementioned laser diffraction/diffusion size distribution analyser, the median size that is suspended in this liquid is 0.5 micron.In addition, add 0.5 grams per liter Starso 7-hydrate reagent, obtain the regulator solution of desiring to apply.[embodiment 17]
The solution of zinc sulfate of 100 milliliter of 1 mol and 100 milliliter of 1 mol 1-sodium hydrogen phosphate solution alternately make an addition under 50 ℃ in 1 liter of 0.5 mol ferrous sulfate (II) solution, to produce sediment.The solution that contains sediment kept 1 hour so that the sediment maturation rinsing 10 times of tilting afterwards down in 90 ℃.After the filtration and the universe are dry, find that by the X-ray diffraction analysis this sediment is phosphoric acid phyllite (Zn
2Fe (PO
4)
24H
2O), part contains tertiary iron phosphate.Make an addition to the 10 weight % aqueous solution of the listed aqueous high molecular compound of 500 gram tables 7 in 100 these phosphoric acid phyllites of gram, in ball mill, use 0.5 mm dia zirconium dioxide bead to grind about 1 hour.After the grinding, use tap water that the phosphoric acid phyllite density in the suspension is transferred to 1 grams per liter and prepares the employed regulator solution of this embodiment.Measure with aforementioned laser diffraction/diffusion size distribution analyser, the median size that is suspended in this liquid is 0.5 micron.[embodiment 18]
In the 10 weight % aqueous solution of the listed aqueous high molecular compound of 1 kilogram of table 7, add 50 gram Zn
3(PO
4)
24H
2O reagent uses 0.5 mm dia zirconium dioxide bead to grind in ball mill about 1 hour.After the grinding, use tap water with the Zn in the liquid
3(PO
4)
24H
2O density transfers to 1 grams per liter.After the adjustment, the median size in the liquid is measured with aforementioned laser diffraction/diffusion size distribution analyser, and the median size that is suspended in this liquid is 0.5 micron.In addition, add 0.5 grams per liter sal epsom, 7 hydrate reagent, obtain the regulator solution of desiring to apply.[embodiment 19]
1 liter of 0.1 mol ca nitrate soln is in 50 ℃ of zinc nitrate solution and 200 milliliter of 1 mol 1-sodium hydrogen phosphates that add 200 milliliter of 1 mol down, to make it sedimentation.The solution that contains sediment kept 1 hour so that the sediment maturation rinsing 10 times of tilting afterwards down in 90 ℃.After the filtration and the universe are dry, find that by the X-ray diffraction analysis this sediment is scholzite (Zn
2Ca (PO
4)
22H
2O).In the 10 weight % aqueous solution of the listed aqueous high molecular compound of 1 kilogram of table 7, add 500 these scholzites of gram, in ball mill, use 10 mm dia zirconium dioxide beads to grind about 1 hour.After the grinding, use tap water that the scholzite density in the suspension is transferred to 5 grams per liters.Measure with aforementioned laser diffraction/diffusion size distribution analyser, the median size that is suspended in this liquid is 1.6 microns.In addition, the yellow soda ash reagent that adds 5 grams per liters obtains the regulator solution of desiring to apply as alkali.[embodiment 20]
1 liter of 0.1 mol ca nitrate soln is in 50 ℃ of zinc nitrate solution and 200 milliliter of 1 mol 1-sodium hydrogen phosphates that add 200 milliliter of 1 mol down, to make it sedimentation.The solution that contains sediment kept 1 hour so that the sediment maturation rinsing 10 times of tilting afterwards down in 90 ℃.After the filtration and the universe are dry, find that by the X-ray diffraction analysis this sediment is scholzite (Zn
2Ca (PO
4)
22H
2O).In 1 kilogram of this scholzite, add the 10 weight % aqueous solution of the listed aqueous high molecular compound of 10 gram tables 7, in ball mill, use 0.5 mm dia zirconium dioxide bead to grind about 1 hour.After the grinding, use tap water that the scholzite density in the suspension is transferred to 30 grams per liters.Measure with aforementioned laser diffraction/diffusion size distribution analyser, the median size that is suspended in this liquid is 0.3 micron.In addition, add the tertiary sodium phosphate reagent of 10 grams per liters as the polyoxyethylene of alkali and 2 grams per liters-ninth of the ten Heavenly Stems phenolic ether as tensio-active agent, adjusted liquid.In the case, under the situation of not degreasing, use test piece, to clean simultaneously and to regulate.[Comparative Examples 6]
The solution of zinc sulfate of 100 milliliter of 1 mol and 100 milliliter of 1 mol 1-sodium hydrogen phosphate solution alternately make an addition under 50 ℃ in 1 liter of 0.5 mol ferrous sulfate (II) solution, to produce sediment.The solution that contains sediment kept 1 hour so that the sediment maturation rinsing 10 times of tilting afterwards down in 90 ℃.After the filtration and the universe are dry, find that by the X-ray diffraction analysis this sediment is phosphoric acid phyllite (Zn
2Fe (PO
4)
24H
2O), part contains tertiary iron phosphate.This phosphoric acid phyllite ground in mortar about 2 minutes.After the grinding,,, abandon filtrate with 5 microns filter paper filterings with the tap water dilution.The sediment of gained becomes powder in dry 1 hour of 80 ℃ of following universes.In 10 weight % solution of the listed aqueous high molecular compound of 500 gram tables 2, add the dry powder of 100 these universes of gram, the dry powder of this universe is transferred to density 1 grams per liter and prepares regulator solution with tap water.When using aforementioned laser diffraction/diffusion size distribution analyser to measure, the median size in the liquid is 6.5 microns.
Table 8 is listed the characteristic of the formed phosphate layer of regulator solution of use table 7.Table 4 is listed the formed phosphate layer characteristic of regulator solution of Comparative Examples 6.
According to table 8 and 4 as can be known, regulator solution of the present invention significantly improves weather resistance.The result of Comparative Examples 3 and embodiment 17 understands the high-performance that shows the aqueous high molecular compound.Though it is Comparative Examples 3 is poor than embodiment 16, good than the liquid commonly used of Comparative Examples 1.
Yet in Comparative Examples 3, the phosphatic pulverizing of divalence or trivalent metal is difficulty very, and, after 10 days, find the phosphoric acid salt sedimentation of divalence or trivalent metal in this liquid preparation.This is because Comparative Examples 3 aquosity macromolecular compound not, so the phosphate powder of this divalence or trivalent metal is condensed.
Table 9 is listed the composition of the regulator solution of claim 4 of the present invention.The acceleration composition of table 9 and Comparative Examples 7 uses monoammonium sulfate to prepare as catalyzer.Though the present invention is not limited pH, if the pH of polymkeric substance or multipolymer is too low, then preferably use sodium hydroxide that the pH of polymkeric substance or multipolymer is transferred to neutrality in advance, be dissolved in the liquid again to prevent phosphate powder.Endurance test is carried out in regulator solution keeps 10 under room temperature after.[embodiment 21]
The solution of zinc sulfate of 100 milliliter of 1 mol and 100 milliliter of 1 mol 1-sodium hydrogen phosphate solution alternately make an addition under 50 ℃ in 1 liter of 0.5 mol ferrous sulfate (II) solution, to produce sediment.The solution that contains sediment kept 1 hour so that the sediment maturation rinsing 10 times of tilting afterwards down in 90 ℃.After the filtration and the universe are dry, find that by the X-ray diffraction analysis this sediment is phosphoric acid phyllite (Zn
2Fe (PO
4)
24H
2O), part contains tertiary iron phosphate.In 1 kilogram of this phosphoric acid phyllite, add 1 gram by the listed polymkeric substance of dilution table in advance 9 or the 10 weight % aqueous solution of multipolymer gained, in ball mill, use 0.5 mm dia zirconium dioxide bead to grind about 1 hour.After the grinding, use tap water that the phosphoric acid phyllite density in the suspension is transferred to 10 grams per liters and prepares the employed regulator solution of this embodiment.Measure with aforementioned laser diffraction/diffusion size distribution analyser, the median size that is suspended in this liquid is 0.5 micron.In addition, add 0.5 grams per liter Sodium Nitrite reagent, obtain the regulator solution of desiring to apply as alkali.[embodiment 22]
The solution of zinc sulfate of 100 milliliter of 1 mol and 100 milliliter of 1 mol 1-sodium hydrogen phosphate solution alternately make an addition under 50 ℃ in 1 liter of 0.5 mol ferrous sulfate (II) solution, to produce sediment.The solution that contains sediment kept 1 hour so that the sediment maturation rinsing 10 times of tilting afterwards down in 90 ℃.After the filtration and the universe are dry, find that by the X-ray diffraction analysis this sediment is phosphoric acid phyllite (Zn
2Fe (PO
4)
24H
2O), part contains tertiary iron phosphate.In 10 weight % dilute aqueous solns of 500 listed polymkeric substance of gram tables 9 or multipolymer, add 100 these phosphoric acid phyllites of gram, in ball mill, use 0.5 mm dia zirconium dioxide bead to grind about 1 hour.After the grinding, use tap water that the phosphoric acid phyllite density in the suspension is transferred to 1 grams per liter and prepares the employed regulator solution of this embodiment.Measure with aforementioned laser diffraction/diffusion size distribution analyser, the median size that is suspended in this liquid is 0.5 micron.[embodiment 23]
The solution of zinc sulfate of 100 milliliter of 1 mol and 100 milliliter of 1 mol 1-sodium hydrogen phosphate solution alternately make an addition under 50 ℃ in 1 liter of 0.5 mol ferrous sulfate (II) solution, to produce sediment.The solution that contains sediment kept 1 hour so that the sediment maturation rinsing 10 times of tilting afterwards down in 90 ℃.After the filtration and the universe are dry, find that by the X-ray diffraction analysis this sediment is phosphoric acid phyllite (Zn
2Fe (PO
4)
24H
2O), part contains tertiary iron phosphate.In the 10 weight % aqueous solution of listed polymkeric substance of 1 kilogram of table 9 or multipolymer, add 25 these phosphoric acid phyllites of gram, in ball mill, use 0.5 mm dia zirconium dioxide bead to grind about 1 hour.After the grinding, use tap water that the phosphoric acid phyllite density in the suspension is transferred to 0.5 grams per liter and prepares the employed regulator solution of this embodiment.Measure with aforementioned laser diffraction/diffusion size distribution analyser, the median size that is suspended in this liquid is 0.5 micron.In addition, add the sal epsom 7-hydrate reagent of 0.5 grams per liter, obtain required regulator solution.[embodiment 24]
1 liter of 0.1 mol ca nitrate soln is in 50 ℃ of zinc nitrate solution and 200 milliliter of 1 mol 1-sodium hydrogen phosphates that add 200 milliliter of 1 mol down, to make it sedimentation.The solution that contains sediment kept 1 hour so that the sediment maturation rinsing 10 times of tilting afterwards down in 90 ℃.After the filtration and the universe are dry, find that by the X-ray diffraction analysis this sediment is scholzite (Zn
2Ca (PO
4)
22H
2O).In 1 kilogram of this scholzite, add the listed polymkeric substance of 1.5 gram tables 9 or the 10 weight % aqueous solution of multipolymer, in ball mill, use 0.5 mm dia zirconium dioxide bead to grind about 1 hour.After the grinding, use tap water that the scholzite density in the suspension is transferred to 10 grams per liters.Measure with aforementioned laser diffraction/diffusion size distribution analyser, the median size that is suspended in this liquid is 0.6 micron.In addition, the yellow soda ash reagent that adds 0.5 grams per liter obtains required regulator solution as alkali.[embodiment 25]
1 liter of 0.1 mol ca nitrate soln is in 50 ℃ of zinc nitrate solution and 200 milliliter of 1 mol 1-sodium hydrogen phosphates that add 200 milliliter of 1 mol down, to make it sedimentation.The solution that contains sediment kept 1 hour so that the sediment maturation rinsing 10 times of tilting afterwards down in 90 ℃.After the filtration and the universe are dry, find that by the X-ray diffraction analysis this sediment is scholzite (Zn
2Ca (PO
4)
22H
2O).In 1 kilogram of this scholzite, add the listed polymkeric substance of 20 gram tables 9 or the 10 weight % aqueous solution of multipolymer, in ball mill, use 0.5 mm dia zirconium dioxide bead to grind about 1 hour.After the grinding, use tap water that the scholzite density in the suspension is transferred to 5 grams per liters.Measure with aforementioned laser diffraction/diffusion size distribution analyser, the median size that is suspended in this liquid is 0.6 micron.In addition, the tertiary sodium phosphate reagent that adds 10 grams per liters obtains required regulator solution as alkali.[embodiment 26]
In 10 weight % solution of listed polymkeric substance of 1 kilogram of table 9 or multipolymer, add 1 kilogram of Zn
3(PO
4)
24H
2O reagent uses 10 mm dia zirconium dioxide beads to grind in ball mill about 1 hour.After the grinding, use tap water with the Zn in the liquid
3(PO
4)
24H
2O density transfers to 1 grams per liter.Measure with aforementioned laser diffraction/diffusion size distribution analyser, the median size that is suspended in the prepared liquid is 1.2 microns.In addition, the Starso reagent that adds 5 grams per liters is as alkali, adds the polyoxyethylene of 2 grams per liters-ninth of the ten Heavenly Stems phenolic ether as tensio-active agent, obtains the regulator solution of desiring to apply.In the case, under not degreasing, use test piece, clean simultaneously and regulate.[embodiment 27]
In 1 kilogram of Zn
3(PO
4)
22H
2In the O reagent, add the polymkeric substance of 50 gram tables 9 or the 10 weight % aqueous solution of multipolymer, in ball mill, use 0.5 mm dia zirconium dioxide bead to grind about 1 hour.After the grinding, use tap water with the Zn in the liquid
3(PO
4)
22H
2O density transfers to 1 grams per liter.After the adjustment, the median size in the liquid is measured with aforementioned laser diffraction/diffusion size distribution analyser, and the median size that is suspended in this liquid is 0.5 micron.[Comparative Examples 7]
The solution of zinc sulfate of 100 milliliter of 1 mol and 100 milliliter of 1 mol 1-sodium hydrogen phosphate solution alternately make an addition under 50 ℃ in 1 liter of 0.5 mol ferrous sulfate (II) solution, to produce sediment.The solution that contains sediment kept 1 hour so that the sediment maturation rinsing 10 times of tilting afterwards down in 90 ℃.After the filtration and the universe are dry, find that by the X-ray diffraction analysis this sediment is phosphoric acid phyllite (Zn
2Fe (PO
4)
24H
2O), part contains tertiary iron phosphate.This phosphoric acid phyllite ground in mortar about 2 minutes.After the grinding,,, abandon filtrate with 5 microns filter paper filterings with the tap water dilution.The sediment of gained becomes powder in dry 1 hour of 80 ℃ of following universes.In the dry sedimentation powder of 1 kilogram of universe, add listed polymkeric substance of 100 gram tables 2 or 10 weight % solution of multipolymer.With tap water this phosphoric acid phyllite particle is transferred to density 1 grams per liter and prepares regulator solution.Use aforementioned laser diffraction/diffusion size distribution analyser to measure, the median size in the liquid is 6.5 microns.
Table 10 is listed the characteristic of the formed phosphate layer of regulator solution that uses embodiment.Table 4 is listed and is used the formed phosphate layer characteristic of Comparative Examples 7 regulator solution.
According to table 10 and 4 as can be known, to make be that the weather resistance of common technology shortcoming is significantly improved to regulator solution of the present invention originally.Relatively the result of Comparative Examples 3 and embodiment 22 and 27 understands the influence that shows this polymkeric substance or multipolymer.
Though Comparative Examples 3 is poor than embodiment 21, have the surface modulation effect good or suitable than the liquid commonly used of Comparative Examples 1.Yet in Comparative Examples 3, the phosphatic pulverizing of divalence or trivalent metal is difficulty very, and, after this liquid prepares 10, the phosphoric acid salt sedimentation of divalence or trivalent metal.This is because do not contain compound or multipolymer, so the phosphoric acid salt of this divalence or trivalent metal condenses once more.The advantage of invention
As mentioned before, regulator solution of the present invention improves the weather resistance of titanium colloid regulator solution, and successfully makes the crystallization of phosphate layer thinner than common technology.Therefore, the present invention has the advantage than common technology economy, and successfully makes the phosphate layer that character is better than common technology.Table 1
| The embodiment numbering | |||||||||||
| ????1 | ????2 | ????3 | ????4 | ????5 | ????6 | ????7 | ????8 | ????9 | ????10 | ||
| The metal tripolyphosphate salt particle | Composition | Zn 2Fe(PO 4) 2·4H 2O | Zn 2Fe(PO 4) 2·4H 2O | Zn 2Fe(PO 4) 2·4H 2O | Zn 2Fe(PO 4) 2·4H 2O | Zn 2Fe(PO 4) 2·4H 2O | Zn 2Fe(PO 4) 2·4H 2O | Zn 3(PO 4) 2·4H 2O | Zn 3(PO 4) 2·4H 2O | Zn 2Ca(PO 4) 2·2H 2O | Zn 2Ca(PO 4) 2·2H 2O |
| ??(g/L) | ?????1 | ?????1 | ??????1 | ??????1 | ??????1 | ??????1 | ??????1 | ?????1 | ??????10 | ??????5 | |
| ??(μm) | ????0.5 | ????0.5 | ?????0.5 | ?????0.5 | ?????0.5 | ?????0.5 | ?????0.6 | ????1.2 | ?????0.4 | ?????0.4 | |
| Single candy, polysaccharide and derivative | Basic structure | Glucose | Glucose | Glucose | Glucose | Glucose | The glucose and xylose semi-lactosi | Glucose | Glucose | Glucose | Glucose |
| Substituting group | ??CH 2COOH ????NO 2 | ??CH 2COOH ????NO 2 | ???CH 2COOH | ??????- | ???????- | ??????- | ???CH 2COOH | ???C 3H 5OH ?????CH 3 | ????C 2H 4OH | ??????- | |
| Substitution value | ????1.8≥ | ???1.8≥ | ?????0.7 | ??????0 | ???????0 | ??????0 | ?????2≤ | ?????1.9 | ?????1.0 | ??????0 | |
| The polymerization degree | ???3000≥ | ???3000≥ | ????100≥ | ??????1 | ?????100≥ | ?????500≥ | ????200≥ | ????1000≥ | ????2000≥ | ?????500≥ | |
| ??(ppm) | ?????5 | ???1000 | ?????10 | ????2000 | ?????2000 | ?????100 | ?????100 | ??????1 | ??????10 | ???????5 | |
| Alkali salt | Composition | ?????- | ?????- | ????NaNO 2 | ????MgSO 4????·7H 2O | ??????- | ??????- | ??????- | Na 2O·SiO 2??·5H 2O | ????Na 2CO 3 | ????Na 3PO 4???·12H 2O |
| ??(ppm) | ?????- | ?????- | ?????0.5 | ?????0.5 | ??????- | ??????- | ??????- | ??????5 | ??????1 | ??????10 | |
| Tensio-active agent | Composition | ?????- | ?????- | ??????- | ??????- | ??????- | ??????- | ??????- | ??????- | ??????- | ??????*1 |
| ??(g/L) | ?????- | ?????- | ??????- | ??????- | ??????- | ??????- | ??????- | ??????- | ??????- | ??????2.0 | |
| Temperature (℃) | ?????20 | ?????20 | ??????20 | ??????20 | ??????20 | ??????20 | ??????20 | ?????20 | ??????20 | ??????40 | |
| Time (second) | ?????30 | ?????30 | ??????30 | ??????30 | ??????30 | ??????30 | ??????30 | ?????30 | ??????30 | ??????120 | |
1
*: polyoxyethylene-phenolic ether in the ninth of the ten Heavenly Stems (E011) table 2
| The reference examples numbering | ||||||||
| ???1 | ?????2 | ??????3 | ???????4 | ??????5 | ??????6 | ?????7 | ||
| Composition | PL-ZN *2 | PL-ZN *2 | Zn 2Fe(PO 4) 2·4H 2O | Zn 2Fe(PO 4) 2·4H 2O | Zn 2Fe(PO 4) 2·4H 2O | Zn 2Fe(PO 4) 2·4H 2O | Zn 2Fe(PO 4) 2·4H 2O | |
| (g/L) | ???1 | ????1 | ?????1 | ???????1 | ??????1 | ??????1 | ?????1 | |
| (μm) | ???- | ????- | ????0.5 | ??????6.5 | ?????6.5 | ?????6.5 | ????6.5 | |
| Basic structure | ???- | ????- | ?????- | Glucose | ??????- | ??????- | ?????- | |
| Substituting group | ???- | ????- | ????? | CH 2COOH NO 2 | ??????- | ??????- | ?????- | |
| Substitution value | ???- | ????- | ?????- | ?????1.8≥ | ??????- | ??????- | ?????- | |
| The polymerization degree | ???- | ????- | ?????- | ????3000≥ | ??????- | ??????- | ?????- | |
| (ppm) | ???- | ????- | ?????- | ??????5 | ??????- | ??????- | ?????- | |
| Phosphorus compound | The organic phospho acid compound | ???- | ????- | ?????- | ??????- | ?????*3 | ??????- | ?????- |
| The aqueous high molecular compound | ???- | ????- | ?????- | ??????- | ??????- | ?????*4 | ?????- | |
| Formula 1 monomer | ????R 1 | ???- | ????- | ?????- | ??????- | ??????- | ??????- | ????CH 3 |
| ????R 2 | ???- | ????- | ?????- | ??????- | ??????- | ??????- | ???C 2H 5 | |
| ????(wt％) | ???- | ????- | ?????- | ??????- | ??????- | ??????- | ????20 | |
| α, β-unsaturated monomer | Composition | ???- | ????- | ?????- | ??????- | ??????- | ??????- | Maleic acid |
| ????(wt％) | ???- | ????- | ?????- | ??????- | ??????- | ??????- | ????30 | |
| Copolymerisable monomer | Composition | ???- | ????- | ?????- | ??????- | ??????- | ??????- | Vinyl sulfonic acid |
| ????(wt％) | ???- | ????- | ?????- | ??????- | ??????- | ??????- | ????50 | |
| Multipolymer | ????(ppm) | ???- | ????- | ?????- | ??????- | ??????- | ??????- | ????10 |
| Alkali salt | Composition | ???- | MgSO 4·7H 2O | ?????- | ??????- | ??????- | ??????- | ?????- |
| ????(g/L) | ???- | ????0.5 | ?????- | ??????- | ??????- | ??????- | ?????- | |
| Tensio-active agent | Composition | ???- | ????- | ?????- | ??????- | ??????- | ??????- | ?????- |
| ????(g/L) | ???- | ????- | ?????- | ??????- | ??????- | ??????- | ?????- | |
| Temperature | ????(℃) | ???20 | ????20 | ?????20 | ??????20 | ??????20 | ??????20 | ?????20 |
| Time | (second) | ???30 | ????30 | ?????30 | ??????30 | ??????30 | ??????30 | ?????30 |
*2: regulator solution commonly used
*3: amido trimethylene phosphonic (500ppm)
*4: the characteristic of the polyvinyl alcohol of carboxyl substituted (500ppm) table 3 embodiment phosphate layer
The characteristic of phosphate layer in table 4 reference examples
Table 5
The characteristic of phosphate layer among table 6 embodiment
Table 7
The characteristic of table 8 embodiment phosphate layer
Table 9
The characteristic of table 10 embodiment phosphate layer
| The embodiment numbering | ||||||||||||
| ????1 | ????2 | ????3 | ????4 | ????5 | ????6 | ????7 | ????8 | ????9 | ????10 | |||
| The preparation back is measured in real time | Outward appearance | ????SPC | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ |
| ????EG | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ||
| ????GA | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ||
| ????Al | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ||
| ???Zn-Ni | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ||
| ????MP | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ||
| ?C.W.(g/m 2) | ????SPC | ????1.6 | ????1.7 | ????1.5 | ????1.6 | ????1.6 | ????1.6 | ????1.5 | ????1.7 | ????1.4 | ????1.5 | |
| ????EG | ????1.7 | ????1.9 | ????1.8 | ????1.7 | ????1.8 | ????1.7 | ????1.6 | ????1.7 | ????1.6 | ????1.7 | ||
| ????GA | ????2.2 | ????2.4 | ????2.4 | ????2.3 | ????2.6 | ????2.7 | ????2.5 | ????2.4 | ????2.6 | ????2.4 | ||
| ????Al | ????1.9 | ????1.8 | ????1.8 | ????1.9 | ????1.6 | ????1.7 | ????1.7 | ????1.6 | ????1.7 | ????1.7 | ||
| ???Zn-Ni | ????1.6 | ????1.7 | ????1.6 | ????1.5 | ????1.6 | ????1.6 | ????1.7 | ????1.8 | ????1.6 | ????1.8 | ||
| ????MP | ????2.5 | ????2.6 | ????2.5 | ????2.7 | ????2.6 | ????2.7 | ????2.5 | ????2.6 | ????2.6 | ????2.7 | ||
| ?C.S.(μm) | ????SPC | ????1～2 | ????1～2 | ????1～2 | ????1～2 | ????1～2 | ????1～2 | ????1～2 | ????1～2 | ????1≥ | ????1～2 | |
| ????EG | ????1～2 | ????1～2 | ????1～2 | ????1～2 | ????1～2 | ????1～2 | ????1～2 | ????1～2 | ????1～2 | ????1～2 | ||
| ????GA | ????2～3 | ????2～3 | ????2～3 | ????2～3 | ????2～3 | ????2～3 | ????2～3 | ????2～3 | ????1～2 | ????2～3 | ||
| ????Al | ????1～2 | ????1～2 | ????1～2 | ????1～2 | ????1～2 | ????1～2 | ????1～2 | ????1～2 | ????1～2 | ????1～2 | ||
| ???Zn-Ni | ????1～2 | ????1～2 | ????1～2 | ????1～2 | ????1～2 | ????1～2 | ????1～2 | ????1～2 | ????1～2 | ????1～2 | ||
| ????MP | ????2～3 | ????2～3 | ????2～3 | ????2～3 | ????2～3 | ????2～3 | ????2～3 | ????2～3 | ????2～3 | ????2～3 | ||
| P ratio (%) | ????SPC | ?????95 | ?????96 | ?????97 | ?????96 | ?????93 | ?????92 | ?????92 | ?????91 | ?????90 | ?????91 | |
| Prepared back 10 days | Outward appearance | ????SPC | ?????◎ | ?????◎ | ?????◎ | ?????◎ | ?????◎ | ?????◎ | ?????◎ | ?????◎ | ?????◎ | ?????◎ |
| ?C.W.(g/m 2) | ????SPC | ????1.5 | ????1.6 | ????1.6 | ????1.6 | ????1.6 | ????1.5 | ????1.5 | ????1.7 | ????1.5 | ????1.5 | |
| ?C.S.(μm) | ????SPC | ????1～2 | ????1～2 | ????1～2 | ????1～2 | ????1～2 | ????1～2 | ????1～2 | ????1～2 | ????1～2 | ????1～2 | |
| P ratio (%) | ????SPC | ?????96 | ?????96 | ?????95 | ?????97 | ?????95 | ?????92 | ?????91 | ?????91 | ?????92 | ?????90 | |
| The Comparative Examples numbering | |||||||||
| ????1 | ????2 | ????3 | ????4 | ????5 | ????6 | ????7 | |||
| The preparation back is instant to be measured | Outward appearance | ????SPC | ????◎ | ????× | ????○ | ???×× | ???×× | ???×× | ???×× |
| ????EG | ????◎ | ????△ | ????◎ | ????△ | ????△ | ????△ | ????△ | ||
| ????GA | ????◎ | ????○ | ????◎ | ????△ | ????△ | ????△ | ????△ | ||
| ????Al | ????× ???????? | ???×× | ????△ | ???×× | ???×× | ???×× | ???×× | ||
| ???Zn-Ni | ????◎ | ????◎ | ????◎ | ????△ | ????△ | ????△ | ????△ | ||
| ????MP | ????○ | ????× | ????◎ | ????○ | ????○ | ????○ | ????○ | ||
| ?C.W.(g/m 2) | ????SPC | ????2.4 | ????3.8 | ????2.0 | ?????- | ?????- | ?????- | ?????- | |
| ????EG | ????2.7 | ????3.2 | ????2.8 | ????3.8 | ????3.9 | ????3.8 | ????4.0 | ||
| ????GA | ????3.1 | ????3.5 | ????3.3 | ????4.4 | ????4.2 | ????4.3 | ????4.7 | ||
| ????Al | ????0.9 | ?????- | ????1.3 | ?????- | ?????- | ?????- | ?????- | ||
| ??Zn-Ni | ????2.5 | ????3.3 | ????2.7 | ????3.6 | ????3.4 | ????3.5 | ????3.5 | ||
| ????MP | ????3.6 | ????1.8 | ????2.8 | ????3.3 | ????3.4 | ????3.5 | ????3.3 | ||
| ?C.S.(μm) | ????SPC | ???3～4 | ????10＜ | ???2～3 | ?????- | ?????- | ?????- | ?????- | |
| ????EG | ???3～4 | ????7～8 | ???2～3 | ????10＜ | ????10＜ | ????10＜ | ????10＜ | ||
| ????GA | ???5～6 | ???7～10 | ???3～4 | ????10＜ | ????10＜ | ????10＜ | ????10＜ | ||
| ????Al | ???4～5 | ?????- | ???2～3 | ?????- | ?????- | ?????- | ?????- | ||
| ???Zn-Ni | ???3～4 | ????6～9 | ???2～3 | ????10＜ | ????10＜ | ????10＜ | ????10＜ | ||
| ????MP | ???5～6 | ???8～10 | ???3～4 | ????5～6 | ????5～6 | ????5～6 | ????5～6 | ||
| P ratio (%) | ????SPC | ????93 | ?????- | ????95 | ?????- | ?????- | ?????- | ?????- | |
| Prepared back 10 days | Outward appearance | ????SPC | ????× | ????×× | ????△ | ????×× | ????×× | ????×× | ????×× |
| ?C.W.(g/m 2) | ????SPC | ????3.3 | ?????- | ????2.8 | ?????- | ?????- | ?????- | ?????- | |
| ?C.S.(μm) | ????SPC | ???7～8 | ?????- | ???3～4 | ?????- | ?????- | ?????- | ?????- | |
| P ratio (%) | ????SPC | ????- | ?????- | ????92 | ?????- | ?????- | ?????- | ?????- | |
| The embodiment numbering | |||||||
| ????11 | ????12 | ????13 | ????14 | ??????15 | |||
| The metal tripolyphosphate salt particle | Composition | Zn 2Fe(PO 4) 2·4H 2O | Zn 2Fe(PO 4) 2·4H 2O | Zn 2Fe(PO 4) 2·4H 2O | Zn 3(PO 4) 2·4H 2O | Zn 2Ca(PO 4) 2·2H 2O | |
| ??(g/L) | ????5 | ????1 | ????1 | ????5 | ????10 | ||
| ??(μm) | ????0.5 | ????0.5 | ????1.7 | ????0.6 | ????0.5 | ||
| Phosphorus compound | Orthophosphoric acid salt, poly-phosphate | Composition | Tripolyphosphate | Six phosphoric acid | ????- | ????- | ????- |
| ??(ppm) | ????1 | ????100 | ????- | ????- | ????- | ||
| The organic phospho acid compound | Composition | ????- | ????- | Amido trimethylammonium phosphonic acids | 1-hydroxy ethylene-1, the 1-di 2 ethylhexyl phosphonic acid | Ethylenediamine tetraacetic ethylidene phosphonic acids | |
| ??(ppm) | ????- | ????- | ????500 | ????50 | ????1000 | ||
| Alkali salt | Composition | ????MgSO 4· ????7H 2O | Na 2O·SiO 2· ????5H 2O | ????- | ????Na 2CO 3 | ????Na 3PO 4· ????12H 2O | |
| ??(g/L) | ????0.5 | ????1 | ????- | ????5 | ????10 | ||
| Tensio-active agent | Composition | ????- | ????- | ????- | ????- | Polyoxyethylene-ninth of the ten Heavenly Stems phenolic ether) (E011) | |
| ??(g/L) | ????- | ????- | ????- | ????- | ????2.0 | ||
| Temperature (℃) | ????20 | ????20 | ????20 | ????20 | ????40 | ||
| Time (second) | ????30 | ????30 | ????30 | ????30 | ????120 | ||
| The embodiment numbering | |||||||
| ????11 | ????12 | ????13 | ????14 | ????15 | |||
| The preparation back is measured in real time | Outward appearance | ????SPC | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ |
| ????EG | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ||
| ????GA | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ||
| ????Al | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ||
| ???Zn-Ni | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ||
| ????MP | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ||
| C.W.(g/m 2) | ????SPC | ????1.7 | ????1.6 | ????1.8 | ????1.7 | ????1.7 | |
| ????EG | ????1.8 | ????1.8 | ????1.9 | ????1.8 | ????1.7 | ||
| ????GA | ????2.3 | ????2.2 | ????2.3 | ????2.2 | ????2.3 | ||
| ????Al | ????1.7 | ????1.7 | ????1.7 | ????1.6 | ????1.7 | ||
| ???Zn-Ni | ????1.6 | ????1.6 | ????1.7 | ????1.6 | ????1.7 | ||
| ????MP | ????2.5 | ????2.4 | ????2.6 | ????2.5 | ????2.7 | ||
| C.S.(μm) | ????SPC | ???1～2 | ???1～2 | ???1～2 | ???1～2 | ???1～2 | |
| ????EG | ???1～2 | ???1～2 | ???1～2 | ???1～2 | ???1～2 | ||
| ????GA | ???2～3 | ???2～3 | ???2～3 | ???2～3 | ???2～3 | ||
| ????Al | ???1～2 | ???1～2 | ???1～2 | ???1～2 | ???1～2 | ||
| ???Zn-Ni | ???1～2 | ???1～2 | ???1～2 | ???1～2 | ???1～2 | ||
| ????MP | ???2～3 | ???2～3 | ???2～3 | ???2～3 | ???2～3 | ||
| P ratio (%) | ????SPC | ????97 | ????97 | ????93 | ????92 | ????93 | |
| Prepared back 10 days | Outward appearance | ????SPC | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ |
| C.W.(g/m 2) | ????SPC | ????1.7 | ????1.7 | ????1.7 | ????1.7 | ????1.6 | |
| C.S.(μm) | ????SPC | ???1～2 | ???1～2 | ???1～2 | ???1～2 | ???1～2 | |
| P ratio (%) | ????SPC | ????97 | ????96 | ????95 | ????93 | ????93 | |
| The embodiment numbering | |||||||
| ???????16 | ?????????17 | ???????18 | ????19 | ????20 | |||
| The metal tripolyphosphate salt particle | Composition | Zn 2Fe(PO 4) 2·4H 2O | Zn 2Fe(PO 4) 2·4H 2O | Zn 3(PO 4) 2·4H 2O | Zn 2Ca(PO 4) 2·2H 2O | Zn 2Ca(PO 4) 2·2H 2O | |
| ????(g/L) | ????????5 | ?????????1 | ???????1 | ?????5 | ????30 | ||
| ????(μm) | ??????0.5 | ????????0.5 | ??????0.5 | ????1.6 | ????0.3 | ||
| The aqueous high molecular compound | The polymkeric substance of vinyl acetate base or derivative | Composition | Polyvinyl alcohol | The polyvinyl alcohol of carboxyl substituted | The polyvinyl alcohol that sulfonic acid replaces | ?????- | ?????- |
| Monomeric multipolymer | Monomer | ???????- | ?????????- | ???????- | Maleic acid | Ba Dousuan | |
| Monomer (wt%) | ???????- | ?????????- | ???????- | ????80 | ????70 | ||
| Total amount | ???(ppm) | ???????1 | ????????500 | ?????2000 | ???1000 | ????30 | |
| Alkali salt | Composition | Na 2O·SiO 2·5H 2O | ?????????- | MgSO 4· 7H 2O | Na 2CO 3 | Na 3PO 4· 12H 2O | |
| ???(g/L) | ??????0.5 | ?????????- | ??????0.5 | ?????5 | ????10 | ||
| Tensio-active agent | Composition | ???????- | ?????????- | ???????- | ?????- | Polyoxyethylene--phenolic ether in the ninth of the ten Heavenly Stems (E011) | |
| ???(g/L) | ???????- | ?????????- | ???????- | ?????- | ????2.0 | ||
| Temperature (℃) | ???????20 | ?????????20 | ???????20 | ?????20 | ?????40 | ||
| Time (second) | ???????30 | ?????????30 | ???????30 | ?????30 | ????120 | ||
| The embodiment numbering | |||||||
| ????16 | ????17 | ????18 | ????19 | ????20 | |||
| The preparation back is measured in real time | Outward appearance | ????SPC | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ |
| ????EG | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ||
| ????GA | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ||
| ????Al | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ||
| ???Zn-Ni | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ||
| ????MP | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ||
| C.W.(g/m 2) | ????SPC | ????1.7 | ????1.6 | ????1.7 | ????1.8 | ????1.4 | |
| ????EG | ????1.8 | ????1.7 | ????1.8 | ????1.9 | ????1.6 | ||
| ????GA | ????2.4 | ????2.2 | ????2.3 | ????2.4 | ????2.2 | ||
| ????Al | ????1.7 | ????1.7 | ????1.8 | ????1.9 | ????1.7 | ||
| ???Zn-Ni | ????1.6 | ????1.5 | ????1.6 | ????1.7 | ????1.5 | ||
| ????MP | ????2.7 | ????2.6 | ????2.8 | ????2.6 | ????2.5 | ||
| C.S.(μm) | ????SPC | ???1～2 | ???1～2 | ???1～2 | ???1～2 | ????1≥ | |
| ????EG | ???1～2 | ???1～2 | ???1～2 | ???1～2 | ???1～2 | ||
| ????GA | ???2～3 | ???2～3 | ???2～3 | ???2～3 | ???2～3 | ||
| ????Al | ???1～2 | ???1～2 | ???1～2 | ???1～2 | ???1～2 | ||
| ??Zn-Ni | ???1～2 | ???1～2 | ???1～2 | ???1～2 | ???1～2 | ||
| ????MP | ???2～3 | ???2～3 | ???2～3 | ???2～3 | ???2～3 | ||
| P ratio (%) | ????SPC | ????97 | ????97 | ????93 | ????92 | ????93 | |
| Prepared back 10 days | Outward appearance | ????SPC | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ |
| C.W.(g/m 2) | ????SPC | ????1.6 | ????1.7 | ????1.7 | ????1.7 | ????1.5 | |
| C.S.(μm) | ????SPC | ???1～2 | ???1～2 | ???1～2 | ???1～2 | ???1～2 | |
| P ratio (%) | ????SPC | ????96 | ????97 | ????92 | ????92 | ????93 | |
| The embodiment numbering | ||||||||
| ??????21 | ???????22 | ??????23 | ???????24 | ???????25 | ?????26 | ?????27 | ||
| Metal phosphate: particle | Composition | Zn 2Fe(PO 4) 2·4H 2O | Zn 2Fe(PO 4) 2·4H 2O | Zn 2Fe(PO 4) 2·4H 2O | Zn 2Ca(PO 4) 2·2H 2O | Zn 2Ca(PO 4) 2·2H 2O | Zn 3(PO 4) 2·4H 2O | Zn 3(PO 4) 2·4H 2O |
| ????(g/L) | ??????10 | ????????1 | ??????0.5 | ???????10 | ???????5 | ??????1 | ?????1 | |
| ????(μm) | ?????0.5 | ???????0.5 | ??????0.5 | ??????0.6 | ??????0.6 | ?????1.2 | ????0.5 | |
| Formula 1 monomer | ????R 1 | ??????H | ????????- | ???????- | ??????CH 3 | ??????CH 3 | ??????H | ?????- |
| ????R 2 | ????C 2H 4OH | ????????- | ???????- | ?????C 3H 7OH | ??????C 2H 5 | ??????H | ?????- | |
| ????(wt％) | ?????100 | ????????- | ???????- | ???????20 | ???????20 | ?????70 | ?????- | |
| α, β-unsaturated monomer | Composition | ??????- | Maleic acid | Vinylformic acid | Maleic acid | Maleic acid | Maleic acid | Methacrylic acid |
| ????(wt％) | ??????- | ???????80 | ?????100 | ???????80 | ???????30 | ?????30 | ?????50 | |
| Comonomer | Composition | ??????- | The vinyl acetate base | ??????- | ???????- | Vinyl sulfonic acid | ??????- | Styrene sulfonic acid |
| ????(wt％) | ??????- | ???????20 | ??????- | ???????- | ???????50 | ??????- | ?????50 | |
| Multipolymer | ????(ppm) | ??????1 | ??????500 | ????2000 | ?????1500 | ???????10 | ?????100 | ??????5 |
| Alkali salt | Composition | ????NaNO 2 | ???????- | ????MgSO 4· ????7H 2O | ?????Na 2CO 3 | ?????Na 3PO 4· ??????12H 2O | ??Na 2O·SiO 2????·5H 2O | ??????- |
| ????(g/L) | ?????0.5 | ???????- | ?????0.5 | ??????0.5 | ???????10 | ??????5 | ??????- | |
| Tensio-active agent | Composition | ??????- | ???????- | ??????- | ???????- | ???????- | Polyoxyethylene-phenolic ether in the ninth of the ten Heavenly Stems (E01 1) | ??????- |
| ????(g/L) | ??????- | ???????- | ??????- | ???????- | ???????- | ?????20 | ??????- | |
| Temperature (℃) | ??????20 | ???????20 | ??????20 | ???????20 | ???????20 | ?????40 | ?????20 | |
| Time (second) | ??????30 | ???????30 | ??????30 | ???????30 | ???????30 | ????120 | ?????30 | |
| The embodiment numbering | |||||||||
| ????21 | ????22 | ????23 | ????24 | ????25 | ????26 | ????27 | |||
| The preparation back is measured in real time | Outward appearance | ????SPC | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ |
| ????EG | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ||
| ????GA | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ||
| ????Al | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ||
| ??Zn-Ni | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ||
| ????MP | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ||
| C.W.(g/m 2) | ????SPC | ????1.4 | ????1.7 | ????1.7 | ????1.5 | ????1.7 | ????1.7 | ????1.6 | |
| ????EG | ????1.6 | ????1.8 | ????1.8 | ????1.7 | ????1.9 | ????1.9 | ????1.7 | ||
| ????GA | ????2.2 | ????2.3 | ????2.3 | ????2.3 | ????2.4 | ????2.4 | ????2.5 | ||
| ????Al | ????1.7 | ????1.8 | ????1.8 | ????1.9 | ????1.8 | ????1.7 | ????1.9 | ||
| ??Zn-Ni | ????1.5 | ????1.7 | ????1.6 | ????1.5 | ????1.7 | ????1.6 | ????1.6 | ||
| ????MP | ????2.5 | ????2.5 | ????2.4 | ????2.6 | ????2.5 | ????2.7 | ????2.5 | ||
| C.S.(μm) | ????SPC | ????1≥ | ???1～2 | ???1～2 | ????1≥ | ???1～2 | ???1～2 | ???1～2 | |
| ????EG | ???1～2 | ???1～2 | ???1～2 | ???1～2 | ???1～2 | ???1～2 | ???1～2 | ||
| ????GA | ???2～3 | ???2～3 | ???2～3 | ???2～3 | ???2～3 | ???2～3 | ???1～2 | ||
| ????Al | ???1～2 | ???1～2 | ???1～2 | ???1～2 | ???1～2 | ???1～2 | ???1～2 | ||
| ??Zn-Ni | ???1～2 | ???1～2 | ???1～2 | ???1～2 | ???1～2 | ???1～2 | ???1～2 | ||
| ????MP | ???2～3 | ???2～3 | ???2～3 | ???2～3 | ???2～3 | ???2～3 | ???2～3 | ||
| P ratio (%) | ????SPC | ????97 | ????96 | ????97 | ????92 | ????91 | ????93 | ????90 | |
| Prepared back 10 days | Outward appearance | ????SPC | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ | ????◎ |
| C.W.(g/m 2) | ????SPC | ????1.5 | ????1.7 | ????1.6 | ????1.6 | ????1.6 | ????1.8 | ????1.5 | |
| C.S.(μm) | ????SPC | ???1～2 | ???1～2 | ???1～2 | ???1～2 | ???1～2 | ???1～2 | ???1～2 | |
| P ratio (%) | ????SPC | ????96 | ????97 | ????96 | ????92 | ????93 | ????91 | ????94 | |
Claims (10)
1. one kind is used for pre-treatment is carried out to form the regulator solution of phosphate layer in the metallic surface, it is characterized in that it contains a kind of or more than the phosphate particle of a kind of divalence or trivalent metal, and contain a kind of or, be selected from single candy, polysaccharide and derivative thereof more than a kind of acceleration composition.
2. one kind is used for pre-treatment is carried out to form the regulator solution of phosphate layer in the metallic surface, it is characterized in that it contains a kind of or more than the phosphate particle of a kind of divalence or trivalent metal, and contain a kind of or, be selected from orthophosphoric acid salt, polyphosphate and organic phospho acid compound more than a kind of acceleration composition.
3. one kind is used for pre-treatment is carried out to form the regulator solution of phosphate layer in the metallic surface, it is characterized in that it contains a kind of or more than the phosphate particle of a kind of divalence or trivalent metal, and contain a kind of or quicken composition more than a kind of water soluble polymer compound, be selected from polymkeric substance, its derivative of vinyl acetate base, and vinyl acetate base and other monomeric multipolymers.
4. one kind is used for preliminary treatment is carried out to form the regulator solution of phosphate layer in the metal surface; It is characterized in that it contains a kind of or more than the phosphate particle of a kind of divalence or trivalent metal; And contain a kind of more than a kind of acceleration composition; Be selected from by the following monomer i of polymerization) and be lower than the following monomer ii of 50 % by weight) polymer or the copolymer of gained; Monomer i): the monomer shown in the following formula (1) or be selected from α-, the monomer of β-unsaturated carbon acid monomers; Monomer ii): can with monomer i) monomer of copolymerization
Wherein, R
1: H or CH
3, R
2: H or have the alkyl of C1～5 or have the hydroxyalkyl of C1～5.
According in the claim 1～4 each be used for pre-treatment is carried out to form the regulator solution of phosphate layer in the metallic surface, it is characterized in that phosphate particle contains diameter less than 5 microns particle, its total concn is 0.001～30 grams per liter, and divalence or trivalent metal are a kind of or more than a kind of metal that is selected from Zn, Fe, Mn, Ni, Co, Ca and Al.
According in the claim 1～5 each be used for pre-treatment is carried out to form the regulator solution of phosphate layer in the metallic surface, the total concn that it is characterized in that quickening composition is 1～2000ppm.
According in the claim 1～6 each be used for pre-treatment is carried out to form the regulator solution of phosphate layer in the metallic surface, it is characterized in that regulator solution contains an alkali metal salt and/or ammonium salt and/or its mixture in addition.
According to claim 7 be used for pre-treatment is carried out to form the regulator solution of phosphate layer in the metallic surface, it is characterized in that alkali metal salts or ammonium salt is a kind of or more than a kind of salt that is selected from orthophosphoric acid salt, metaphosphate, ortho-silicate, metasilicate, carbonate, supercarbonate, nitrate, nitrite, vitriol, borate and organic acid salt, and its total concn is 0.5～20 grams per liter.
9. one kind is used to carry out the method for pre-treatment with the adjusting metallic surface of formation phosphate layer, it is characterized in that the metallic surface contacts with each regulator solution in the claim 1～8 earlier before forming phosphate layer.
10. be used to carry out the method for pre-treatment according to claim 9 with the adjusting metallic surface that forms phosphate layer, it is characterized in that regulator solution contains alkaline constituents and a kind of or more than a kind of additive in addition, be selected from nonionic surfactant and anionic surfactant, so that regulator solution has other effects on clean metal surface.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP204635/98 | 1998-07-21 | ||
| JP20463598 | 1998-07-21 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1242436A true CN1242436A (en) | 2000-01-26 |
| CN1265024C CN1265024C (en) | 2006-07-19 |
Family
ID=16493750
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB991106601A Expired - Lifetime CN1265024C (en) | 1998-07-21 | 1999-07-21 | Conditioning liquid and conditioning process used in pretreatment for forming of phosphate layer on metallic surface |
Country Status (5)
| Country | Link |
|---|---|
| KR (1) | KR100609482B1 (en) |
| CN (1) | CN1265024C (en) |
| ID (1) | ID23566A (en) |
| MY (1) | MY129412A (en) |
| TW (1) | TW491912B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104018149A (en) * | 2014-06-11 | 2014-09-03 | 张家港保税区冠祥贸易有限公司 | Phosphating solution for surface pretreatment of metal product and preparation method of phosphating solution |
| CN104328402A (en) * | 2014-10-23 | 2015-02-04 | 苏州莱特复合材料有限公司 | Phosphating solution for tungsten-base powder metallurgical materials and preparation method thereof |
| CN109072442A (en) * | 2016-04-25 | 2018-12-21 | Ppg工业俄亥俄公司 | Reactivity purificant and method for handling substrate |
| CN114761618A (en) * | 2019-11-26 | 2022-07-15 | 汉高股份有限及两合公司 | Resource-saving method for activating metal surface before phosphating |
| US11518960B2 (en) | 2016-08-24 | 2022-12-06 | Ppg Industries Ohio, Inc. | Alkaline molybdenum cation and phosphonate-containing cleaning composition |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5520439B2 (en) * | 2007-11-01 | 2014-06-11 | 日本パーカライジング株式会社 | Method for producing surface-adjusted aluminum casting |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4012795A1 (en) * | 1990-04-21 | 1991-10-24 | Metallgesellschaft Ag | ACTIVATING AGENT FOR PHOSPHATING |
-
1999
- 1999-07-14 MY MYPI99002962A patent/MY129412A/en unknown
- 1999-07-20 ID IDP990683A patent/ID23566A/en unknown
- 1999-07-20 KR KR1019990029301A patent/KR100609482B1/en not_active IP Right Cessation
- 1999-07-20 TW TW088112333A patent/TW491912B/en not_active IP Right Cessation
- 1999-07-21 CN CNB991106601A patent/CN1265024C/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104018149A (en) * | 2014-06-11 | 2014-09-03 | 张家港保税区冠祥贸易有限公司 | Phosphating solution for surface pretreatment of metal product and preparation method of phosphating solution |
| CN104328402A (en) * | 2014-10-23 | 2015-02-04 | 苏州莱特复合材料有限公司 | Phosphating solution for tungsten-base powder metallurgical materials and preparation method thereof |
| CN109072442A (en) * | 2016-04-25 | 2018-12-21 | Ppg工业俄亥俄公司 | Reactivity purificant and method for handling substrate |
| US11518960B2 (en) | 2016-08-24 | 2022-12-06 | Ppg Industries Ohio, Inc. | Alkaline molybdenum cation and phosphonate-containing cleaning composition |
| CN114761618A (en) * | 2019-11-26 | 2022-07-15 | 汉高股份有限及两合公司 | Resource-saving method for activating metal surface before phosphating |
| CN114761618B (en) * | 2019-11-26 | 2024-03-19 | 汉高股份有限及两合公司 | Resource saving method for activating metal surface before phosphating |
Also Published As
| Publication number | Publication date |
|---|---|
| MY129412A (en) | 2007-03-30 |
| TW491912B (en) | 2002-06-21 |
| KR100609482B1 (en) | 2006-08-09 |
| CN1265024C (en) | 2006-07-19 |
| ID23566A (en) | 2000-05-04 |
| KR20000011838A (en) | 2000-02-25 |
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