CN1451702A - Organic silicon modified cathode electrophoresis epoxy coating and process for preparing same - Google Patents
Organic silicon modified cathode electrophoresis epoxy coating and process for preparing same Download PDFInfo
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- CN1451702A CN1451702A CN 03114338 CN03114338A CN1451702A CN 1451702 A CN1451702 A CN 1451702A CN 03114338 CN03114338 CN 03114338 CN 03114338 A CN03114338 A CN 03114338A CN 1451702 A CN1451702 A CN 1451702A
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Abstract
An organosilicon modified epoxy paint for cathode electrophoresis is prepared through modifying epoxy resin by aminosilicone oil and organic amine compound respectively, adding full-closed polyisocyanate as cross-linking agent, neutralizing by organic acid, and emulsifying-dispersing in water medium. Its advantages are smooth surface of its coated film, adjustable film thickness, excellent high-temp resistance, and high electrophoresist penetrability and electric deposition stability.
Description
Technical field
The present invention relates to a kind of electrophoretic paint technology, particularly a kind of organic silicon modified epoxy oxygen cathode electrophoretic paint and preparation method thereof.
Background technology
The history in existing more than 100 year of the development of electrophoretic paint, early stage exploitation mainly concentrates on the anode electrophoresis dope, but it is found that in actual applications there is the dissolving anode in anodic electrophoretic coating technology, promptly is coated with the shortcoming of object.Cathode electrophoresis dope is to grow up the seventies in 20th century and obtain a kind of novel anticorrosive coating of industrial applications, since cathode electrophoresis dope have good non-corrosibility, high throwing power, application level of automation height, environmental pollution little, do not dissolve advantages such as coated article, tank liquor be stable, make it obtain widespread use as priming paint in automotive industry.Along with the development of technology, cathode electrophoresis dope overflows and to all conglomeraties such as household electrical appliance, toy, instrument, military project, building materials, its application also no longer is confined to the protection against corrosion of material, but has the surface decoration effect of material concurrently.
Along with the continuous development and progress of electrophoretic paint technology, people are to the demands for higher performance of coating.Therefore, in conjunction with the matrix material that forms, will give coated article with multiple material with new surface property.Organosilicon polymer makes it have the not available excellent properties of many other materials because there is special Si-O-Si structure in its main chain, and is very big as Si-O key bond energy, reaches 452KJ/mol, and thermostability is fine; Electrical property changes little in wide temperature range (50～200 ℃); Surface energy is low.Organic-silicon-modified various organic synthetic resin, as alkyd, epoxy, vinylformic acid, polyester, urethane etc., can improve guarantor's light weathering resistance, the hydrophobic water tolerance of these synthetic resin paints significantly, can be used as durable coating, maintenance lacquer and the weather resistance finish paint for building of household electrical appliance finish paint, high-quality antifouling paste, coil coating, outdoor structural part respectively.Modifying epoxy resin by organosilicon both can reduce the Resins, epoxy internal stress, can increase Resins, epoxy toughness again, improved the thermotolerance and the mechanical property of resin, reduced the surface energy of coating simultaneously.Silicone resin is introduced the epoxy cathode electrophoresis dope, and expection can obtain having the excellent chemical resistant properties and the electro-deposited film of low surface energy.Some typical water-base epoxy cathode electrophoresis dopes are disclosed in CN1339535A, CN1226913A, CN1094739A, CN1074027C, CN1052320A, we have applied for the preparation method's of polytetrafluoroethylmodified modified low surface energy epoxy cathode electrophoresis dope patent (CN1400255A), up to the present, do not see the report of organic silicon modified epoxy oxygen cathode electrophoretic paint.
Summary of the invention
The objective of the invention is to overcome the shortcoming of prior art, a kind of organic silicon modified epoxy oxygen cathode electrophoretic paint is provided, be characterized in that the paint film that obtains after this electrophoretic paint galvanic deposit has excellent chemical resistant properties, high heat resistance and low surface energy.
Another object of the present invention is to provide a kind of method for preparing above-mentioned organic silicon modified epoxy oxygen cathode electrophoretic paint.
Purpose of the present invention is achieved through the following technical solutions.The preparation method of this organic silicon modified epoxy oxygen cathode electrophoretic paint comprises the steps: that Resins, epoxy is respectively after amido silicon oil and organic amine compound modification, add totally-enclosed polyisocyanate crosslinker, in the organic acid neutralizing agent and after, emulsification disperses to prepare organic silicon modified epoxy oxygen cathode electrophoretic paint in aqueous medium.
The weight ratio of described Resins, epoxy, amido silicon oil, totally-enclosed polyisocyanate crosslinker is 20～60: 5～50: 10～50.
Described Resins, epoxy is bisphenol A type epoxy resin of different molecular weight and composition thereof, and its epoxy equivalent (weight) is 200～4000.
Described amido silicon oil is that side chain contains amino small molecules silane, kinematic viscosity 200～5000mm
2/ s (25 ℃), amino content 0.2～1.2%.
Being prepared as follows of described totally-enclosed polyisocyanate crosslinker: in the presence of organotin catalysts, with the totally-enclosed polyisocyanate crosslinker of encapsulant prepared in reaction of polyisocyanates with the band reactive hydrogen.Described polyisocyanates is compounds such as tolylene diisocyanate, '-diphenylmethane diisocyanate, hexamethylene diisocyanate and composition thereof; Described encapsulant is single ether class of alcohols, dibasic alcohol, the macromole polyether polymer of polyvalent alcohol and compound of other band reactive hydrogen and composition thereof, as ethanol, butanols, Virahol, isopropylcarbinol, ethylene glycol monobutyl ether; Described organotin catalysts is stannous octoate, Dibutyltin oxide, dibutyl tin dilaurate etc., and dibutyl tin dilaurate is preferred.The preparation of some typical totally-enclosed polyisocyanate crosslinkers is also disclosed in CN1074027C.
Described organic amine compound is diethylamine, dibutylamine, Monoethanolamine MEA BASF, diethanolamine, Mono Methyl Ethanol Amine or above-mentioned amine mixture, and diethanolamine is preferred; The consumption of aforementioned organic amine compound is based on 45～85 equivalent % of epoxy total amount.
Described organic acid neutralizing agent consumption is 2～5% of Resins, epoxy, amido silicon oil, a totally-enclosed polyisocyanate crosslinker gross weight; Described organic acid neutralizing agent can adopt formic acid, acetate, oxyacetic acid, methanesulfonic, ethane sulfonic acid, propane sulfonic acid, hydroxyethanesulfonic acid, hydroxypropanesulfonic acid or its mixture, and acetate and methanesulfonic are preferred.
Organic silicon modified epoxy oxygen cathode electrophoretic paint of the present invention can adopt existing universal high speed dispersion machine or special-purpose emulsifying machine to carry out dispersion and emulsion by aforesaid method to prepare.
The present invention has following advantage with respect to prior art: the more different organosilicon content modified epoxy cathode electrophoresis dopes and the performance of existing epoxy cathode electrophoresis dope, find that it is that 18 ± 2% water miscible liquid can directly be carried out electrophoretic painting that modifying epoxy resin by organosilicon of the present invention and deionized water (specific conductivity＜15 μ s/cm) are made into solid, its pH value is 6.0 ± 0.5, specific conductivity is 1500 ± 500 μ s/cm, 50～300 volts of electrophoretic voltages, electrophoresis temperature is 25～30 ℃, and electrodeposition time is 1～5 minute; Paint film solidified 10～30 minutes at 130～180 ℃; It is evenly smooth to make appearance of film, and feel is sliding, and thickness is adjustable in 15～40 μ m, Good Heat-resistance, and the surface contact angle water is measured as 60～120 ° (size of contact angle is to weigh the standard the most easily of surface energy, and contact angle is big, and then surface energy is low); In addition, organic silicon modified epoxy oxygen cathode electrophoretic paint of the present invention also has higher permeability ratio and galvanic deposit stability preferably.
Description of drawings
The cataphoretic coating TG graphic representation of Fig. 1 organic silicon modified epoxy oxygen cathode of the present invention electrophoretic paint (A: the cataphoretic coating TG curve of organic silicon modified epoxy oxygen cathode electrophoretic paint of the present invention; B: the cataphoretic coating TG curve of unmodified epoxy cathode electrophoresis dope).
Embodiment
Below by embodiment the present invention is done further concrete description, but embodiments of the present invention are not limited thereto.
Embodiment 1
(1) preparation of totally-enclosed polyisocyanate crosslinker
(1) prescription title specification parts by weight toluene di-isocyanate(TDI) 2,4 bodies or mixture 116.4 ethylene glycol monoethyl ethers industry 39.0 ethylene glycol monobutyl ethers industry 90.0 polyethers N-204 industry 27.0 polyethers N-210 industry 13.5 dibutyl tin dilaurate chemical pures 0.3
(2) preparation technology
In being housed, the dry reaction still of thermometer, agitator, reflux exchanger adds tolylene diisocyanate and dibutyl tin dilaurate, after being warming up to 40 ℃, stirring begins to drip ethylene glycol monoethyl ether and ethylene glycol monobutyl ether, be warming up to 70 ℃ then, reacted 2 hours, add polyethers N-204 and polyethers N-210 more successively, be warming up to 110 ℃, reacted 2.5 hours, sampling is surveyed free NCO content with infrared spectra, less than 2% is qualified, be cooled to 60 ℃ at last with bottom discharge, in the airtight container of drying, preserve standby.
(2) preparation of organic silicon modified epoxy oxygen cathode electrophoretic paint
(1) prescription title specification parts by weight epoxy resin CYD-014; 100.0 ethylene glycol monobutyl ethers industry, the 33.0 amido silicon oil industry of Yueyang petrochemical industry epoxy resin factory, 5.0 diethanol amine industry, the 11.0 totally-enclosed polyisocyanates embodiment 1 35.0 lactic acid industry 7.0 of Jiangxi spark Materials Co., Ltd
(2) preparation technology
Thermometer is being housed, agitator, the ethylene glycol monobutyl ether that adds formula ratio in the reactor of reflux exchanger, add Resins, epoxy and insulation under 120 ℃ after being warming up to 80 ℃, treat to cool to below 80 ℃ after it dissolves evenly fully, add amido silicon oil, 90～100 ℃ were reacted 2 hours down, cool to again below 80 ℃ and add diethanolamine, 90～100 ℃ were reacted 2 hours down, cool to again and add totally-enclosed polyisocyanates below 80 ℃, be warmed up to 110 ℃ of reactions 3.5～4 hours, cool to then below 70 ℃, add neutralizing agent lactic acid, stir standby after 1～2 hour.
Reaction solution is transferred in the clean emulsion tank, added deionized water, lactic acid, emulsification 2 hours is filtered, and promptly makes the electrophoresis emulsion.
Ability cathode electrophoresis technology is adopted in test, and the coated article iron plate is hung on negative electrode, and anode is a stainless steel substrates; The coated article iron plate all needed to transfer (colloid peptide)-a series of operations such as washing-phosphatization to carry out pre-treatment through oil removing-washing-rust cleaning-washing-neutralization-washing-Biao before galvanic deposit, and electrophoretic voltage is 80V, and electrodeposition time is 2 minutes.After galvanic deposit was finished, taking-up had the iron plate elder generation immersion tap water of filming and removes the lacquer liquid that remains in the surface, uses distilled water flushing again, solidifies 30 minutes at 160 ℃ afterwards.It is evenly smooth to make appearance of film, feel is sliding, in the thickness 28.5 μ m, the acid-fast alkali-proof excellent performance, the water surface contact angle is 70 °, surface energy lower (see Table 1, the performance of the unmodified epoxy cathode electrophoresis dope cataphoretic coating of attached the same terms is so that contrast), thermotolerance height (see TG thermogravimetric curve A among Fig. 1, the TG thermogravimetric curve B of the unmodified epoxy cathode electrophoresis dope cataphoretic coating of attached the same terms is so that contrast).
Table 1
| The epoxy cathode electrophoresis dope | 5% amino-modified silicone epoxy cathode electrophoresis dope embodiment 1 | 10% amino-modified silicone epoxy cathode electrophoresis dope embodiment 2 | 20% amino-modified silicone epoxy cathode electrophoresis dope embodiment 3 | |
| Electrodeposition weight (g/m 2) thickness (μ m) sticking power hardness contact angle (°) | 37.6 29.4 1 grades of 5H 58 | 36.8 28.5 1 grades of 4H 70 | 35.4 28.1 1 grades of 4H 90 | 42.5 32.3 1 grades of 3H 90 |
Embodiment 2
(1) preparation of totally-enclosed polyisocyanate crosslinker
With prescription and preparation technology among the embodiment 1 ().
(2) preparation of organic silicon modified epoxy oxygen cathode electrophoretic paint
(1) prescription title specification parts by weight epoxy resin CYD-014; 100.0 ethylene glycol monobutyl ethers industry, the 33.0 amido silicon oil industry of Yueyang petrochemical industry epoxy resin factory, 10.0 diethanol amine industry, the 10.0 totally-enclosed polyisocyanates embodiment 1 35.0 lactic acid industry 7.0 of Jiangxi spark Materials Co., Ltd
(2) preparation technology
With the technology among the embodiment 1 (two).
Embodiment 3
(1) preparation of totally-enclosed polyisocyanate crosslinker
With executing prescription and preparation technology in the example 1 ().
(2) preparation of organic silicon modified epoxy oxygen cathode electrophoretic paint
(1) prescription title specification parts by weight epoxy resin CYD-014; 100.0 ethylene glycol monobutyl ethers industry, the 33.0 amido silicon oil industry of Yueyang petrochemical industry epoxy resin factory, 20.0 diethanol amine industry, the 8.8 totally-enclosed polyisocyanates embodiment 1 35.0 lactic acid industry 7.0 of Jiangxi spark Materials Co., Ltd
(2) preparation technology
With the technology among the embodiment 1 (two).
The technical indicator of organic silicon modified epoxy oxygen cathode electrophoretic paint of the present invention is:
| Solids content | 36±2％ |
| The pH value | 6.0±0.5 |
| | 100～400cps(25±1℃) |
| Specific conductivity | 1500±500μs/cm(25±1℃) |
Claims (9)
1, a kind of preparation method of organic silicon modified epoxy oxygen cathode electrophoretic paint, it is characterized in that comprising the steps: that Resins, epoxy is respectively after amido silicon oil and organic amine compound modification, add totally-enclosed polyisocyanate crosslinker, in the organic acid neutralizing agent and after, emulsification disperses in aqueous medium.
2, the preparation method of organic silicon modified epoxy oxygen cathode electrophoretic paint according to claim 1 is characterized in that: the weight ratio of described Resins, epoxy, amido silicon oil and totally-enclosed polyisocyanate crosslinker is 20～60: 5～50: 10～50.
3, the preparation method of organic silicon modified epoxy oxygen cathode electrophoretic paint according to claim 1 and 2 is characterized in that: described amido silicon oil, kinematic viscosity 200～5000mm
2/ s, amino content 0.2～1.2%.
4, the preparation method of organic silicon modified epoxy oxygen cathode electrophoretic paint according to claim 1 and 2 is characterized in that: described Resins, epoxy is bisphenol A type epoxy resin and composition thereof, and its epoxy equivalent (weight) is 200～4000.
5, the preparation method of organic silicon modified epoxy oxygen cathode electrophoretic paint according to claim 1 is characterized in that: described organic amine compound is diethylamine, dibutylamine, Monoethanolamine MEA BASF, diethanolamine, Mono Methyl Ethanol Amine, perhaps above-mentioned amine mixture.
6, the preparation method of organic silicon modified epoxy oxygen cathode electrophoretic paint according to claim 5 is characterized in that: described organic amine compound is a diethanolamine, and its consumption is 45～85 equivalent % based on the epoxy total amount.
7, the preparation method of organic silicon modified epoxy oxygen cathode electrophoretic paint according to claim 1 is characterized in that: described organic acid neutralizing agent is formic acid, acetate, oxyacetic acid, methanesulfonic, ethane sulfonic acid, propane sulfonic acid, hydroxyethanesulfonic acid, hydroxypropanesulfonic acid or its mixture.
8, the preparation method of organic silicon modified epoxy oxygen cathode electrophoretic paint according to claim 7, it is characterized in that: described organic acid neutralizing agent is acetate and methanesulfonic, its consumption be Resins, epoxy, amido silicon oil, totally-enclosed polyisocyanate crosslinker gross weight 2～5%.
9, a kind of organic silicon modified epoxy oxygen cathode electrophoretic paint for preparing by the preparation method of the described organic silicon modified epoxy oxygen cathode of claim 1～8 electrophoretic paint.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 03114338 CN1238450C (en) | 2003-04-29 | 2003-04-29 | Organic silicon modified cathode electrophoresis epoxy coating and process for preparing same |
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| CN 03114338 CN1238450C (en) | 2003-04-29 | 2003-04-29 | Organic silicon modified cathode electrophoresis epoxy coating and process for preparing same |
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| CN1238450C CN1238450C (en) | 2006-01-25 |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102040842A (en) * | 2010-10-28 | 2011-05-04 | 华南理工大学 | Autocatalytic crosslinking type organic silicon-epoxy composite material and preparation method thereof |
| CN102071451A (en) * | 2010-10-29 | 2011-05-25 | 江西理工大学 | Electrophoretic preparation method of RCC (resin coated copper foil) |
| CN101368057B (en) * | 2008-09-25 | 2011-09-14 | 江泽平 | High-performance 150 DEG C oven dry type bi-component epoxy-polyurethane cathode electrophoretic paint |
| CN102199786A (en) * | 2010-03-24 | 2011-09-28 | 汉达精密电子(昆山)有限公司 | Method for preventing corrosion of magnesium alloy caused by contacting with dissimilar metal connecting piece |
| CN104004448B (en) * | 2014-05-04 | 2016-07-13 | 四川理工学院 | A kind of one pack system cathode electrophoresis dope for vehicle paint base |
| CN105885510A (en) * | 2016-05-23 | 2016-08-24 | 潍坊合力水性涂料制造有限公司 | Cross-linking agent for electrophoretic paint and production technology of cross-linking agent |
| CN106243311A (en) * | 2016-08-03 | 2016-12-21 | 广东科德环保科技股份有限公司 | A kind of aqueous epoxy resin emulsion and preparation method thereof, cathode electrophoresis dope |
| CN108531048A (en) * | 2018-04-10 | 2018-09-14 | 安徽陵阳新材料有限公司 | A kind of preparation method of edge coverage type electrophoretic paint epoxy acrylic resin base-material |
| CN111019092A (en) * | 2019-12-25 | 2020-04-17 | 芜湖春风新材料有限公司 | Preparation method of organic silicon modified cathode electrophoresis resin and cathode electrophoresis emulsion prepared by same |
| CN115820081A (en) * | 2022-11-15 | 2023-03-21 | 华南理工大学 | Preparation method of water-based super-hydrophobic epoxy resin and application of water-based super-hydrophobic epoxy resin in marine corrosion prevention |
-
2003
- 2003-04-29 CN CN 03114338 patent/CN1238450C/en not_active Expired - Fee Related
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101368057B (en) * | 2008-09-25 | 2011-09-14 | 江泽平 | High-performance 150 DEG C oven dry type bi-component epoxy-polyurethane cathode electrophoretic paint |
| CN102199786A (en) * | 2010-03-24 | 2011-09-28 | 汉达精密电子(昆山)有限公司 | Method for preventing corrosion of magnesium alloy caused by contacting with dissimilar metal connecting piece |
| CN102040842A (en) * | 2010-10-28 | 2011-05-04 | 华南理工大学 | Autocatalytic crosslinking type organic silicon-epoxy composite material and preparation method thereof |
| CN102040842B (en) * | 2010-10-28 | 2012-12-26 | 华南理工大学 | Autocatalytic crosslinking type organic silicon-epoxy composite material and preparation method thereof |
| CN102071451A (en) * | 2010-10-29 | 2011-05-25 | 江西理工大学 | Electrophoretic preparation method of RCC (resin coated copper foil) |
| CN104004448B (en) * | 2014-05-04 | 2016-07-13 | 四川理工学院 | A kind of one pack system cathode electrophoresis dope for vehicle paint base |
| CN105885510A (en) * | 2016-05-23 | 2016-08-24 | 潍坊合力水性涂料制造有限公司 | Cross-linking agent for electrophoretic paint and production technology of cross-linking agent |
| CN106243311A (en) * | 2016-08-03 | 2016-12-21 | 广东科德环保科技股份有限公司 | A kind of aqueous epoxy resin emulsion and preparation method thereof, cathode electrophoresis dope |
| CN108531048A (en) * | 2018-04-10 | 2018-09-14 | 安徽陵阳新材料有限公司 | A kind of preparation method of edge coverage type electrophoretic paint epoxy acrylic resin base-material |
| CN111019092A (en) * | 2019-12-25 | 2020-04-17 | 芜湖春风新材料有限公司 | Preparation method of organic silicon modified cathode electrophoresis resin and cathode electrophoresis emulsion prepared by same |
| CN111019092B (en) * | 2019-12-25 | 2023-04-18 | 芜湖春风新材料有限公司 | Preparation method of organic silicon modified cathode electrophoresis resin and cathode electrophoresis emulsion prepared by same |
| CN115820081A (en) * | 2022-11-15 | 2023-03-21 | 华南理工大学 | Preparation method of water-based super-hydrophobic epoxy resin and application of water-based super-hydrophobic epoxy resin in marine corrosion prevention |
| CN115820081B (en) * | 2022-11-15 | 2024-05-17 | 华南理工大学 | Preparation method of water-based super-hydrophobic epoxy resin and application of water-based super-hydrophobic epoxy resin in marine corrosion prevention |
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|---|---|
| CN1238450C (en) | 2006-01-25 |
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