For stainless steel, the integrally formed surface treatment liquid of plastic cementTechnical field
The present invention relates to method for treating stainless steel surfaces, suitable for stainless steel-plastic cement integral molding techniques, more particularly to exists3C electronic applications machine housing stainless steel links complex with high intensity organic synthetic resin.
Background technology
From the development trend of consumer electronics, the innovation of 3C outward appearances experienced transformation of the plastic cement toward metal chassis, because goldenCategory has entirely different performance in performance and sensuously with plastics.Al-alloy metal casing is quickly grown in recent years, due to itExcellent processing performance, light weight, anode appearance various colors, in 3C shells field using more and more extensive.But anode oxide filmHardness, wearability, the weather resistance shortcoming of layer, the dye coating on surface easily come off with routine use friction, slightly collide with and causeApparent flaws.
In terms of material angle, there is a certain degree of shielding to radio signal in metal chassis；Mobile terminal metal closed loopStructure, clearly, mobile phone will be unable to normal received signal to the effect of electromagnetic shielding, and engineering plastics do not interfere with to wireless signalAnd shielding action, the use of engineering plastics as connection between metal is to select well therefore.
Consumer proposes new demand to the attractive in appearance and texture of electronic product.Stainless steel high intensity, metal surface is high after plated filmHardness, more colored appearances, stainless steel metal housing are expected to turn into the another new breakthrough after aluminium alloy.
At present, the associated methods of stainless steel and organic synthetic resin mainly have 2 kinds, and one kind is will not using Organic adhesiveSteel become rusty together with resin-bonded；It is another to be acted on by chemistry, electrochemical corrosion, corrode in stainless steel surfaces and specific morphologyHole, metal and resin-bonded are got up.However, adhesive adhesion limited strength, subsequent processing operations not acid and alkali-resistance, noSuitable for the seamless combination of stainless steel and plastic cement.
Japanese Yasurou Itou Co., Ltd. is proposed the engineering resin of high intensity in the case of without using bonding agentWith Mg, Al and stainless steel NMT handling process technologies, suitable for polyphenylene sulfide (PPS) and polybutylene terephthalate (PBT) (PBT)Integral forming process.
U.S. Patent number US8784981 introduces a kind of stainless steel and plastic cement PBT, PPS integral forming process method, anode workSkill can be in 1%-10% nitric acid, 10g/L-100g/L iron chloride and additive thiocarbamide about 1g/L-10g/L or sodium potassium tartrate tetrahydrate aboutCarried out in 4g/L-40g/L electrolyte, current density is per 1A/dm2-10A/dm2, the average pore size of stainless steel surfaces perforated membrane100nm-500nm。
Chinese patent CN105500600A discloses a kind of surface treatment technique for stainless steel, using sulfuric acid, citric acid, phosphoric acid notPre-processed with composition, then carry out the electrochemical treatments of alkaline solution or sour row solution immersion treatment.Hole size pointCloth 100-50000nm, hole depth 100-50000nm.
But above different process technology is adapted to be molded with the engineering plastic such as PBT, PPS, but with PAEK PAEKs,The adhesions such as IXEF poly aromatic acid amides are undesirable, so as to limit use range.
The content of the invention
For in the prior art the defects of, study stainless steel metal new surface treatment technologies, suitable for more macromolecules closeResin, manufacture stainless steel-plastic cement one, is achieved by the following technical solution.
One kind is used for stainless steel, the integrally formed surface treatment liquid of plastic cement, and the surface treatment liquid is lost by etchant, auxiliaryAgent, complexing agent, solvent and surfactant composition are carved, wherein, the mass parts of chemical etching liquor total amount 100, coordinate with 20-50 partsThe etchant of mass parts, the etching auxiliary agent of 3-20 part mass parts, the complexing agent of 1-10 part mass parts, 5-20 part mass parts it is moltenAgent and the surfactant of 0.5-3 part mass parts.
Further, etchant is made up of 5%-50% iron chloride, 5%-20% copper sulphate or copper chloride.Wherein, etchThe preferred 15%-30% iron chloride of agent, 10%-20% copper sulphate or copper chloride composition.
Further, assisted etch agent is made up of two or more the mixed acid in hydrochloric acid, sulfuric acid and phosphoric acid, itsIn, on the basis of the mix acid liquor is gross mass, content of hydrochloric acid 3-65%, the sulfuric acid content is 1-15%, the phosphoric acidContent is 0-20%.
Further, complexing agent is by mixture more than one or both of sodium gluconate, EDTA-4Na, citric acidComposition, wherein, on the basis of complexing agent gross mass, gluconic acid sodium content is 1-80%, and EDTA-4Na contents are 1-15%, lemonLemon acid sodium content forms for 1-20%.
Further, solvent is glycerine, glycerol content 5-20%.Wherein, glycerol content is preferably 10-20%.
Further, surfactant is that nonionic surfactant forms with anion surfactant, surface-activeAgent content is 0.1-5%.
Process object suitable for surface treatment liquid is stainless steel, including：Chromium stainless steel, model SUS405, SUS429 or SUS 403；Chromium nickel stainless steel, model SUS301, SUS304, SUS316, SUS305.
After the stainless steel surface treated liquid chemical treatment, corrosion hole, described hole hole are contained on stainless steel surfacesFootpath is distributed as 10-200 μm, and depth is 10-100 μm.
For the present invention in view of the problems of above, its object is to provide a kind of method for treating stainless steel surfaces, the partyMethod is not on the basis of stainless rule cun is corroded, there is provided a kind of adhesion is excellent, production is simple and easy, engineering stability is controllable, lowThe metal-resin integral forming process method of cost.
The present invention chemical pretreatment solution, it is characterized in that coordinated a certain amount of iron ion, copper ion, inorganic acid, complexing agent,Solvent and surfactant composition.
According to the present invention, as long as stainless steel is immersed in above-mentioned treatment fluid, it is possible to formed in metal base surfaceUniform hole, while stainless steel base size is not influenceed.Hole depth is controllable, is adapted to subsequent mechanical CNC, polishing, polishing etc.Process removes, and is advantageous to make appearance decoration.
In above-mentioned chemical pretreatment solution, preferably at least containing iron ion, copper ion, chlorion, hydrogen ion.Pass throughChemical etching forms excellent hole pattern in stainless steel surfaces, while can effectively prevent the general corrosion of stainless steel.Next, forThe mass parts of total amount 100 of chemical pretreatment solution, preferably 15%-30% iron chloride, 10%-20% copper sulphate or copper chloride, 5-20%Mix acid system.
In addition, the treatment fluid containing complexing agent, can improve dissolubility of the metal ion in treatment fluid, can effective control flumeThe effective content of liquid iron ion, copper ion, discharges on demand, at the same be complexed the metal ions such as the nickel corroded, chromium be it is effective,And then provide stable chemical pretreatment solution.For the content 1- of the mass parts of total amount 100, preferably complexing agent of chemical pretreatment solution20%.
Again, the treatment fluid containing solvent and surfactant, can effectively reduce the surface tension of system, and control is stainlessThe hole density on steel substrate surface is effective.
One kind provided by the invention is integrally formed surface treatment liquid for stainless steel-plastic cement, includes by mass concentration followingMaterial：Coordinate with the etchant of 20-50 part mass parts, the etching auxiliary agent of 3-20 part mass parts, the solvents of 5-20 part mass parts withAnd the surfactant of 0.5-3 part mass parts.
Embodiment
Below in conjunction with the embodiment of the present invention, the technical scheme in the content of the invention is clearly and completely described, shownSo, described embodiment is only part of the embodiment of the present invention, rather than whole embodiments.Based on the reality in the present inventionExample is applied, the every other embodiment that those of ordinary skill in the art are obtained under the premise of creative work is not made, is all belonged toIn the scope of protection of the invention.
For technical problem solved by the invention is more clearly understood, with reference to embodiments, the present invention is entered to advanceOne step describes in detail, and specific embodiment described herein is only to parse the present invention, but do not limit the present invention.
Feature of the present invention is can effectively to control etch-hole pattern in stainless steel etching process, does not influence stainless steel size.
One kind provided by the invention is integrally formed surface treatment liquid for stainless steel-plastic cement, has excellent surface corrosionPerformance, processing liquid tank can for a long time be used continuously, add on demand.Include following material by mass concentration：Coordinate with 20-50The etchant of part mass parts, the etching auxiliary agent of 3-20 part mass parts, the solvent and 0.5-3 part mass parts of 5-20 part mass partsSurfactant.If etchant concentration is higher than 50%, insoluble precipitation danger is had, etching action is not had less than 20g/L；ErosionCarve assistant concentration and be less than 3g/L, etching speed is too slow, and higher than 20g/L, it is too many that tank liquor accordingly accumulates the secondary product that responds, and influences tank liquorService life；The preferred 1-20% of complexing agent, iron, copper ion are discharged on demand in tank liquor system, while be complexed the nickel corroded, chromiumIt is effective Deng metal ion, and then provide stable chemical pretreatment solution to bring the hidden danger of general corrosion, solvent and surfaceThe treatment fluid of activating agent, the surface tension of system can be effectively reduced, the hole density on control stainless steel substrate surface is effective.
Stainless steel degreasing, degreasing process include leaching degreasing agent -15 minutes about 5 minutes, and combination Vincellar reaches company's commodityRTS305B, ultrasound is better, if without ultrasound, can air bubbling.Then rinsed in water abundant.
Stainless steel activates, to remove the oxide-film formed on stainless steel surface.The process of activation is included stainless steelAcid solution is immersed in about 1-2min, acid solution room temperature is probably sulfuric acid or hydrochloric acid solution, or its mixture.When using sulphurDuring acid solution, the mass percent of sulfuric acid in an acidic solution is about 15%- 35%.In this exemplary embodiment, stainless steelIt is 1min or so to be immersed in about 15% mass percent, the sulfuric acid solution in activation process, stainless steel surfaces is formedThe native oxide of one layer of iron can be removed effectively, not corrode base material.That is, stainless steel surfaces are not formed in activation processObvious hole or groove.After activation process terminates, stainless steel washing is abundant.
Using specific embodiment, the present invention will be described in further detail below.
Treatment fluid forms：Ferric trichloride 20%, copper sulphate 10%, hydrochloric acid 10%, complexing agent 5%, glycerine 10%, surface are livedProperty agent 0.5%；
As shown in table 1, it is glossing flow, processing test piece is respectively model SUS304, SUS316, SUS316L'sStainless steel, processing procedure are as follows：
Cleaning：The RTs305B solution that by concentration be 10-30%, temperature is 70 ° -80 DEG C, soak the 60-180 seconds, drumBubble；
Washing：Soak 60-180 seconds, bubbling at room temperature by pure water；
Activation：60-180 seconds, bubbling are soaked by the sulfuric acid solution of 15% concentration at room temperature；
Again by above-mentioned water-washing process once；
Etching process：By the surface treatment liquid stoste of the present invention, 180-600 seconds, bubbling are soaked at 60-100 DEG C；
Again by above-mentioned water-washing process once；
Neutralize：It is 10-20%, RTs322 solution at room temperature by concentration, soaks 60-180 seconds, bubbling；
It is secondary by above-mentioned water-washing process again；
Injection moulding process is finally dried again.
Table 1：
Test result such as table 2 below, after stainless steel SUS304, SUS316, SUS316L processing, surface hole defect size is 20-100 μm, pass through pulling force>15MPa test, injection are not glued, and can pass through hot and humid, thermal shock and air tightness test.
Table 2：
Although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be withA variety of changes, modification can be carried out to these embodiments, replace without departing from the principles and spirit of the present invention by understandingAnd modification, the scope of the present invention is defined by the appended.