CN104711567A - Pretreatment liquid for chromium-free passivation on tinplate surface - Google Patents
Pretreatment liquid for chromium-free passivation on tinplate surface Download PDFInfo
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- CN104711567A CN104711567A CN201510117019.9A CN201510117019A CN104711567A CN 104711567 A CN104711567 A CN 104711567A CN 201510117019 A CN201510117019 A CN 201510117019A CN 104711567 A CN104711567 A CN 104711567A
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- titanate
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Abstract
The invention discloses a pretreatment liquid for chromium-free passivation on a tinplate surface, and belongs to the technical field of tinplate surface treatment. The pretreatment liquid comprises the following components in percent by volume: 1.5-2% of tetrabutyl titanate, 75-80% of ethanol, 4-5% of acetylacetone, 3.5-5% of acetic acid, 4-5% of n-butanol and 6-8% of titanate ester, wherein titanate ester is a chelate of bis(P,P-bis-ethylhexyl diphosphato)ethanediolato titanate and triethanolamine, the density of titanate ester is 1.008 g/cm<3>, the pH value of titanate ester is 6.5-7.5, and titanate ester represented as a yellow-red transparent thick liquid can dissolve in lower alcohols and water. The pretreatment liquid adopts a chromium-free formula and is combined by inorganic and organic substances, and a reaction is carried out between inorganic titanium produced through tetrabutyl titanate hydrolysis on the basis of the titanate reacts and the titanate, so that the performance of a conversion coating can be ensured; compared with the tinplate subject to chromium passivation, the tinplate treated by using the pretreatment liquid provided by the invention is higher in corrosion resistance; meanwhile, the adhesion, sulfur resistance and welding requirements can also be met.
Description
Technical field
The invention belongs to tin plate sheet surface processing technology field, be specifically related to a kind of pretreatment liquid for tin plate sheet surface chromium-free deactivation.
Background technology
Tin plate (mainly referring to electrolytic tinplate) is commonly called as tinplate and refers to the steel plate made at the thick mild steel plate plated surface layer of metal tin of 0.10 ~ 0.32mm.Because tin layers is subject to corrosion failure in atmospheric environment, certain sfgd. need be taked to it.Electrolysis sexavalent chrome passivating method is taked in traditional guard method, and its technique is simple, conversion film and basal body binding force good, corrosion resisting property is better.Because sexavalent chrome is carcinogenic substance, have comparatively major injury to human body and environment, therefore its use is subject to larger restriction.Exploitation chromium-free deactivation technology, carry out green industry technology, protection of the environment is industry what the trend requires.
Chinese patent CN 101358342A discloses a kind of brilliant tin plate chromium-free passivation solution, containing 20 ~ 70g tertiary sodium phosphate in often liter of passivating solution, 0.1 ~ 5g rose vitriol, 0.5 ~ 3g Sodium orthomolybdate, 20 ~ 75g phosphoric acid, all the other are water, and passivating solution pH is 3 ~ 5, tin plate passivation effect after treatment with have chromium passivating suitable.Chinese patent CN 101358340A discloses a kind of tin plate chromium-free passivation solution, and wherein often liter of passivating solution contains 20 ~ 70g tertiary sodium phosphate, 0.1 ~ 5g cobalt chloride, 20 ~ 75g phosphoric acid, and all the other are water.Chinese patent CN 101545107A provides a kind of surface treatment liquid for tin plate, wherein containing 1 ~ 50g/L phosphorus compound; 1 ~ 20g/L vanadium compound; 1 ~ 30g/L is selected from one or more compounds in molybdenum, zirconium, titanium, manganese or tungsten metallization compound; 1 ~ 10g/L has one or more compounds of at least one functional group in hydroxyl, carbonyl, carboxyl or phosphate, and the tin plate steel plate of this surface treatment liquid process of process is close in performance chromium passivating process.Chinese patent CN 1416478A application discloses that a kind for the treatment of solution containing phosphate ion, tin ion and silane coupling agent, and not containing chromium in pretreatment liquid provided by the present invention, after coating adhesion, japanning, solidity to corrosion, rust-resisting property and processibility all reach excellent.
The existing patent about Cr-free Passivation for Tin-plated Sheet mainly concentrates on exploitation electrolysis non-chromium inactivating technique, and the bibliographical information about dip-coating and spray non-chromium inactivating technique is little.Because tin plate overall development trend is that the thickness reducing coating ensures that tin plate quality is constant simultaneously, simultaneously for zinc-plated production line, take spray or dipping process to replace electrolysis process and can promote zinc-plated production efficiency.
Summary of the invention
The present invention is directed to the technical problem existed in existing tin plate sheet surface process, a kind of pretreatment liquid for tin plate sheet surface chromium-free deactivation is provided.This pretreatment liquid, can not only ensure tin plate sheet surface quality, reduces conversion film thicknesses of layers simultaneously, reduces tin plate coating integral thickness further.
Component and the volumn concentration thereof of a kind of pretreatment liquid for tin plate sheet surface chromium-free deactivation provided by the present invention are as follows:
Described titanic acid ester is the inner complex of Di(dioctylpyrophosphato) ethylene titanate and trolamine, and its density is 1.008g/cm
3, pH value is 7 ± 0.5; Described titanic acid ester is yellowish red color clear viscous liquids, can be dissolved in lower alcohol and water.
Described pretreatment liquid is prepared by the following method: under normal temperature, and tetrabutyl titanate is dissolved in ethanolic soln, then adds methyl ethyl diketone, acetic acid, propyl carbinol, titanic acid ester successively.Stir after 3 hours and leave standstill use, described pretreatment liquid pH value is 5 ~ 6.
The top condition that described tin plate chromium-free pretreatment liquid is used for tin plate sheet surface is: treatment temp: 25 ~ 30 DEG C; Be coated with ETL estimated time of loading: 15 ~ 30 seconds; Solidification value: 120 DEG C; Set time: 20 ~ 30 seconds.
The coating process flow process that described tin plate chromium-free pretreatment liquid is used for tin plate sheet surface comprises: pre-degreasing → degreasing → washing → oven dry → passivation → solidification.
Evaluate tin plate chromium-free pretreatment liquid of the present invention is formed with zero waste water discharge performance for tin plate sheet surface, mainly the tin plate sheet surface performance after pre-treatment is evaluated.
Evaluation result is obtained by following experiment content:
(1) weldability:
Use the tin plate sheet surface after surface resistivity instrument test application, recording instrumnet display data.Get different sites in triplicate, get evaluation of estimate.
(2) neutral salt spray test:
With reference to GB10125-1997 standard, neutral salt spray test is carried out to paint film.The etchant solution of the experiment of this experiment is 5% sodium chloride solution, pH value of solution=7 (± 0.5), and spray the temperature inside the box is 35 (± 2) DEG C, and sinkability is 2mL/ (80cm
2h), sample and the placement at 45 ° of salt fog frame vertical direction, spraying is after 2 hours continuously, observes workpieces surface condition.Also x-ray fluorescence spectrometry instrument (ARL Advant ' X Intellipower 3600) can be adopted to carry out quantitatively characterizing, and the note S content do not carried out measured by high-temperature heating treatment is S
before,s content measured after process is S
after, make difference △ S=S
after-S
before, and compare △ S (△ S is mass percent increment).
(3) resistance to SO_2:
Tin plate upper surface roller coat PPG2004-827 coating after passivation, dries 12min under 205 DEG C of high temperature, cooling; 14min. is dried again, cooling, each repetition 2 times under 185 DEG C of high temperature.Fill in the inert containers of obtain solution by folding for model being immersed in, seal, solution tool lid inner face should at 5mm to 7mm.Container is placed in pressure kettle, is heated to 121 DEG C and keeps 60min., natural step-down, after cooling, take out print, clean, dry, observe membranaceous condition.
(4) adhesion test:
Sticking power uses the situation of special determinator pull-away in the area that circles that the circle that coating surface draws a string intersection that partly overlaps mutually observes these overlapping intersections surround, and is divided into 7 grades during evaluation.
The present invention has following technical characterstic:
(1) take roller coat or shower coat, substitute traditional electrolysis application, decrease operation, reduce energy consumption;
(2) take complete Chrome-free Recipe, reduce technique to the discharge of chromium element in environment;
(3) in the present invention coating process and the curing process time short, efficiency is high, is conducive to the actual production of factory;
(4) chromium-free treating liquid in the present invention takes Inorganic whisker, the inorganic titanium that the basis of titanic acid ester is produced by tetrabutyl titanate hydrolysis and titanic acid ester are had an effect, fill up and make up its hole, being no more than while 1 μm at thickness, ensureing the performance of conversion film;
(5) through the tin plate of pretreatment liquid process provided by the present invention, its solidity to corrosion performance increases than there being chromium passivating, also meets the requirements such as sticking power, resistance to SO_2, weldability simultaneously.
Embodiment
Embodiment 1: tin plate chromium-free pretreatment liquid is calculated according to 1000ml.At temperature 30 DEG C, 800ml ethanol is added in reactor, after starting stirring, add 15ml tetrabutyl titanate with the speed of 5ml/ minute, uniform stirring added 40ml methyl ethyl diketone, 35ml acetic acid, 40ml propyl carbinol, 60ml titanic acid ester successively with the speed of 5ml/ minute after 30 minutes.
The technical process of Cr-free Passivation for Tin-plated Sheet pre-treatment is: degreasing → washing → alkali cleaning → washing → oven dry → passivation → solidification.
This implementing process is simple, and the pretreatment liquid of configuration is placed without sediment after three months, good stability.The processing parameter of tin plate pre-treatment is 30 seconds time, temperature 120 DEG C.After 2 hours salt mist experiments, tin plate sheet surface is not any change.Sulfur resistance test display surface sulphur spot does not almost have.Surface resistivity is 2.9 × 10
-4Ω, meets welding requirements.It is 1 grade that adhesion test tests out paint film adhesion.
Embodiment 2: tin plate chromium-free pretreatment liquid is calculated according to 1000ml.At temperature 30 DEG C, 750ml ethanol is added in reactor, after starting stirring, add 20ml tetrabutyl titanate with the speed of 5ml/ minute, uniform stirring added 50ml methyl ethyl diketone, 50ml acetic acid, 50ml propyl carbinol, 80ml titanic acid ester successively with the speed of 5ml/ minute after 30 minutes.
The technical process of Cr-free Passivation for Tin-plated Sheet pre-treatment is: degreasing → washing → alkali cleaning → washing → oven dry → passivation → solidification.
This implementing process is simple, and the pretreatment liquid of configuration is placed without sediment after three months, good stability.The processing parameter of tin plate pre-treatment is 30 seconds time, temperature 120 DEG C.After 2 hours salt mist experiments, tin plate sheet surface is not any change.Sulfur resistance test display surface sulphur spot does not almost have.Surface resistivity is 2.402 × 10
-4Ω, meets welding requirements.It is 1 grade that adhesion test tests out paint film adhesion.
Embodiment 3: tin plate chromium-free pretreatment liquid is calculated according to 1000ml.At temperature 30 DEG C, 780ml ethanol is added in reactor, after starting stirring, add 18ml tetrabutyl titanate with the speed of 5ml/ minute, uniform stirring added 45ml methyl ethyl diketone, 38ml acetic acid, 48ml propyl carbinol, 71ml titanic acid ester successively with the speed of 5ml/ minute after 30 minutes.
The technical process of Cr-free Passivation for Tin-plated Sheet pre-treatment is: degreasing → washing → alkali cleaning → washing → oven dry → passivation → solidification.
This implementing process is simple, and the pretreatment liquid of configuration is placed without sediment after three months, good stability.The processing parameter of tin plate pre-treatment is 30 seconds time, temperature 120 DEG C.After 2 hours salt mist experiments, tin plate sheet surface is not any change.Sulfur resistance test display surface sulphur spot does not almost have.Surface resistivity is 1.36 × 10
-4Ω, meets welding requirements.It is 1 grade that adhesion test tests out paint film adhesion.
Embodiment 4: tin plate chromium-free pretreatment liquid is calculated according to 1000ml.At temperature 30 DEG C, 770ml ethanol is added in reactor, after starting stirring, add 20ml tetrabutyl titanate with the speed of 5ml/ minute, uniform stirring added 45ml methyl ethyl diketone, 45ml acetic acid, 45ml propyl carbinol, 75ml titanic acid ester successively with the speed of 5ml/ minute after 30 minutes.
The technical process of Cr-free Passivation for Tin-plated Sheet pre-treatment is: degreasing → washing → alkali cleaning → washing → oven dry → passivation → solidification.
This implementing process is simple, and the pretreatment liquid of configuration is placed without sediment after three months, good stability.The processing parameter of tin plate pre-treatment is 30 seconds time, temperature 120 DEG C.After 2 hours salt mist experiments, tin plate sheet surface is not any change.Sulfur resistance test display surface sulphur spot does not almost have.Surface resistivity is 3.036 × 10
-4Ω, meets welding requirements.It is 1 grade that adhesion test tests out paint film adhesion.
Pretreatment liquid the performance test results prepared by embodiment 1-4 is in table 1.
Table 1: each embodiment the performance test results
Claims (1)
1. for a pretreatment liquid for tin plate sheet surface chromium-free deactivation, it is characterized in that the component of described pretreatment liquid and volumn concentration as follows:
Described titanic acid ester is the inner complex of Di(dioctylpyrophosphato) ethylene titanate and trolamine, and its density is 1.008g/cm
3, pH value is 7 ± 0.5, and described titanic acid ester is yellowish red color clear viscous liquids, can be dissolved in lower alcohol and water; Described pretreatment liquid is prepared by the following method: under normal temperature, described tetrabutyl titanate is dissolved in described ethanolic soln, add described methyl ethyl diketone, acetic acid, propyl carbinol and titanic acid ester successively again, stir after 3 hours and leave standstill use, described pretreatment liquid pH value is 5 ~ 6.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105755454A (en) * | 2016-03-03 | 2016-07-13 | 福建省闽发铝业股份有限公司 | Chromate-free passivation surface treatment agent applied before aluminum profile coating |
| CN107858677A (en) * | 2017-11-22 | 2018-03-30 | 五河县绍峰电器有限公司 | A kind of passivating solution for the surface treatment of fabric air-permeability tester steel workpieces |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101435078A (en) * | 2007-11-13 | 2009-05-20 | Posco公司 | Non-chrome resin composition, method for processing steel plate surface and steel plate |
| CN103695889A (en) * | 2014-01-08 | 2014-04-02 | 安徽工业大学 | Chromium-free passivation solution for surface treatment of galvanized plate, aluminum and copper alloy |
-
2015
- 2015-03-17 CN CN201510117019.9A patent/CN104711567B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101435078A (en) * | 2007-11-13 | 2009-05-20 | Posco公司 | Non-chrome resin composition, method for processing steel plate surface and steel plate |
| CN103695889A (en) * | 2014-01-08 | 2014-04-02 | 安徽工业大学 | Chromium-free passivation solution for surface treatment of galvanized plate, aluminum and copper alloy |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105755454A (en) * | 2016-03-03 | 2016-07-13 | 福建省闽发铝业股份有限公司 | Chromate-free passivation surface treatment agent applied before aluminum profile coating |
| CN107858677A (en) * | 2017-11-22 | 2018-03-30 | 五河县绍峰电器有限公司 | A kind of passivating solution for the surface treatment of fabric air-permeability tester steel workpieces |
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| CN104711567B (en) | 2017-09-29 |
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Effective date of registration: 20200430 Address after: 213000 No. 2 Chuangsheng Road, Luoyang Town, Wujin District, Changzhou City, Jiangsu Province Patentee after: Jiangsu Jiuzhou Packaging Technology Co., Ltd. Address before: 243000 No.5 workshop of Ma'anshan industrial transfer demonstration park, Anhui Province Patentee before: ANHUI QIANHE NEW MATERIAL SCIENCE & TECHNOLOGY DEVELOPMENT Co.,Ltd. |