CN100497408C - Self-deposition coating based on vinylidene chloride-acrylate copolymer latex and preparing method - Google Patents
Self-deposition coating based on vinylidene chloride-acrylate copolymer latex and preparing method Download PDFInfo
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- CN100497408C CN100497408C CNB2007100273102A CN200710027310A CN100497408C CN 100497408 C CN100497408 C CN 100497408C CN B2007100273102 A CNB2007100273102 A CN B2007100273102A CN 200710027310 A CN200710027310 A CN 200710027310A CN 100497408 C CN100497408 C CN 100497408C
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- vinylidene chloride
- acrylate copolymer
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Abstract
The invention discloses an auto deposition coating and its preparation method based on vinylidene chloride-acrylate copolymer latex. This invention takes vinylidene chloride and acrylic as monomers synthesizing vinylidene chloride-acrylate copolymer latex, and then adds paint, hydrogen peroxide, iron powder, HF and deionized water to prepare the auto deposition coating, which can replace electrophoretic paint for the metal substrates, also the automobile body, trailers and small metal pieces.
Description
Technical field
The present invention relates to a kind of coating, specifically, relate to a kind of autodeposition coatings and preparation method based on vinylidene chloride-acrylate copolymer latex.
Background technology
Auto-deposition is the U.S. Am-chem company invention sixties, and begins to be applied to industrial coating in the mid-1970s, and this technology is used very ripe at present.Auto deposition coating (also claiming from the swimming lacquer) is a kind of need not the energising, makes coating cover the full immersed type aqueous coating method of steel surface automatically by chemical reaction.It is made up of water, resin, pigment, oxygenant and acid.The microbattery chemical action that forms in acidic solution by steel part (or other metal) makes (autodeposition coatings) breakdown of emulsion of latex particle in the solution and is attached on the steel part, is formed with as the coating as the powder coating, passes through film-forming again.
The existing many pieces of patents of the U.S. provide synthetic method and the coating compound method that is used to prepare the autodeposition coatings main film forming substance.US6312820 for example, US5385758, US5510410, US4243704, US5061523, US4180603 etc.In these patents, autodeposition coatings is the filmogen of this coating with esters of acrylic acid, polyvinylidene chloride (PVDC) and epoxy resin-matrix mainly.Polyvinylidene chloride is one of three big high barrier polymer materialss of popular in the world today.Owing to its good resistance oxygen, block water, hinder CO
2Performances such as property and oil resistant, chemicals-resistant have been widely used in food product pack and protective system at present.But because there is dehydrochlorination reaction in vinylidene chloride latex, colour stability is bad, and prior art does not all address this problem well.
In U.S. Pat 5352726, US5385758, among the CN1117824C, autodeposition coatings is formulated by polymer latex, hydrogen peroxide, carbon black color slurry, ferrous fluoride (or three ferric fluorides), hydrochloric acid and deionized water.Because three ferric fluorides need import, price is expensive, and the application has substituted three ferric fluorides with inexpensive iron powder.
Summary of the invention
The objective of the invention is to overcome the problem that prior art exists, providing a kind of is that solvent substitutes the poisonous and harmful solvent in the existing coating with water, can adapt to vinylidene chloride-acrylate copolymer latex that automobile metal base material autodeposition coatings is used.
Another object of the present invention provides the preparation method of above-mentioned vinylidene chloride-acrylate copolymer latex.
Further purpose of the present invention is to utilize above-mentioned vinylidene chloride-acrylate copolymer latex, thereby provides cost low, can adapt to the autodeposition coatings of automobile metal base material.
A kind of vinylidene chloride-acrylate copolymer latex is obtained by the component reaction of following weight percentage:
(1) 1,1-Ethylene Dichloride (VDC) 10～90%; 1,1-Ethylene Dichloride is vinylidene chloride.
(2) the category-A reaction monomers 10～80%, and described category-A reaction monomers is one or more the mixture in methyl acrylate (MA), ethyl propenoate (EA), butyl acrylate (BA), methyl methacrylate (MMA), vinyl cyanide (AN), the methacrylonitrile;
(3) the category-B reaction monomers 1～10%, and described category-B reaction monomers is one or more the mixture in vinylformic acid (AA), methacrylic acid (MAA), methylene-succinic acid (ITA), acrylamide (AM), Methacrylamide, N hydroxymethyl acrylamide (NMA), hydroxyethyl methylacrylate (HEMA), the Rocryl 410 (HPMA);
(4) esters of acrylic acid C monomer 0.5～5%, described esters of acrylic acid C monomer are glycidyl methacrylate (GMA) or glytidyl methacrylate or its mixture;
(5) D class reaction monomers 0.5～5%, described D class reaction monomers are one or more the mixture in sodium vinyl sulfonate (SVS of Rhodia company), allyloxy hydroxide sodium dimercaptosulphanatein (COPS-1 of Rhodia company), the hydroxyethyl methacrylate propanesulfonic acid sodium (HPMAS);
(6) emulsifying agent 0.5～5%, described emulsifying agent is one or more the mixture in sodium lauryl sulphate (K12), Sodium dodecylbenzene sulfonate (SDS), alkyl diphenyl base oxide stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonate (2A1 of DOW chemical company), ethoxylated alkylphenol ammonium sulfate (CO-436 of Rhodia company), alkylphenol polyoxyethylene class (as NP-10, NP40, OP-10), the sulfo-succinic acid disodium ethoxylated alcohol half ester (A102 of Cytec company);
(7) initiator 0.1～0.6%, and described initiator is Sodium Persulfate/sodium bisulfite, tertbutyl peroxide/sodium sulfoxylate formaldehyde/Fe
3+, tertbutyl peroxide/saccharosonic acid/Fe
3+, ammonium persulphate (APS), Potassium Persulphate (KPS) or Diisopropyl azodicarboxylate (AIBN);
(8) the molecular chain transfer agent 0.1～0.5%, and described molecular chain transfer agent is tert-dodecyl mercaptan (TDM) or 2 one mercaptoethanol NG or its mixture.
The preparation method of above-mentioned vinylidene chloride-acrylate copolymer latex comprises the steps:
(1) form pre-emulsion: with vinylidene chloride, category-A monomer, category-B monomer, esters of acrylic acid C monomer, D class monomer, emulsifying agent, molecular chain transfer agent and deionized water at room temperature, stirred 0.5 hour, rotating speed 500～600rpm produces pre-emulsion;
(2) seeded emulsion polymerization: in reactor, with deionized water, emulsifier for mixing dissolving, logical nitrogen to reaction system pressure is 0.25MPa, be warmed up to 60 ℃ and add the part initiator, the pre-emulsion of adding 1/10 is as seed emulsion, and question response system blueing light drips residue pre-emulsion and residue initiator simultaneously, with dripping off pre-emulsion in 4 hours, with dripping off initiator in 4.5 hours.
(3) slaking:, be warmed up to 86 ℃ of slakings 0.5 hour, cooling then, release, check, discharging when pre-emulsion and initiator drip off.
The vinylidene chloride that makes-acrylate copolymer latex particle diameter 80～150nm, viscosity 50～60mpa.s/25 ℃, solid content is about 45%.
A kind of autodeposition coatings based on vinylidene chloride-acrylate copolymer latex comprises following component and weight percentage:
(1) vinylidene chloride-acrylate copolymer latex;
(2) dispersible pigment color paste, weight are 1～20% of vinylidene chloride-acrylate copolymer latex;
(3) hydrogen peroxide of concentration 10%, weight are 0.5～10% of vinylidene chloride-acrylate copolymer latex;
(4) iron powder, weight are 0.1～5% of vinylidene chloride-acrylate copolymer latex;
(5) hydrofluoric acid of concentration 10%, weight are 0.5～15% of vinylidene chloride-acrylate copolymer latex;
Each component is mixed, add appropriate amount of deionized water, stir, promptly obtain coating solid content 5～20%, the autodeposition coatings that pH value 2～5 antiseptic properties are good.
Compared with prior art, the present invention has following beneficial effect:
The present invention is a monomer with vinylidene chloride and acrylate, synthetic vinylidene chloride-acrylate copolymer latex, add dispersible pigment color paste, hydrogen peroxide, iron powder, hydrofluoric acid and deionized water again and be mixed with autodeposition coatings, alternative electrocoating paint, be used for the application of metal base, also be applicable to the application of body of a motor car, vehicle frame and smallclothes metal device.Autodeposition coatings paint film cost of the present invention is low, and is good to the metal attachment fastness, antiseptic property is good, salt fog resistance can reach more than 350 hours, shock-resistant, hardness 4H.
Embodiment
Embodiment 1
Earlier synthetic vinylidene chloride-acrylate copolymer latex, its technology is as follows:
With 45.0 the gram deionized waters, 1.2 the gram K12,0.6 the gram NP-10 drop into stir in the reactor after, add 4.0 gram MAA, 2.0 gram HPMAS, 1.0 gram GMA, 26.0 gram BA, 27.0 gram MMA, 37.6 gram VDC and 0.1 gram TDM successively, at room temperature stirred 0.5 hour, rotating speed 500～600rpm forms pre-emulsion.Then in another stainless steel cauldron, with 40.0 gram deionized waters, 0.2 gram K12 stirring and dissolving, logical nitrogen to reaction system pressure is 0.25MPa, be warmed up to 60 ℃ of solution that add 0.06 gram Sodium Persulfate, 0.06 gram sodium bisulfite and 5.0 gram water as initial initiator, the pre-emulsion of adding 1/10 is as seed emulsion, question response system blueing light drips residue pre-emulsion and initiator simultaneously, and this initiator is the solution of 0.09 gram Sodium Persulfate, 0.09 gram sodium bisulfite and 30.0 gram water.With dripping off pre-emulsion in 4 hours, with dripping off initiator in 4.5 hours.When pre-emulsion drips off, be warmed up to 86 ℃ of slakings 0.5 hour, cooling then, release, check, discharging.
Take by weighing quantitative polymer latex then, under agitation add quantitative dispersible pigment color paste, hydrogen peroxide, iron powder, hydrofluoric acid and deionized water at leisure, stirring to make the autodeposition coatings that is applicable to coated metal.The concrete prescription of autodeposition coatings sees Table 1.
Table 1
Embodiment 2
Earlier synthetic vinylidene chloride-acrylate copolymer latex, its technology is as follows:
With 45.0 the gram deionized waters, 1.5 the gram 2A1,0.6 the gram CO-436 drop into stir in the reactor after, add 5.0 gram MAA, 3.0 gram HPMAS, 1.0 gram GMA, 28.0 gram BA, 20.0 gram MMA, 13.0 gram AN, 27.3 gram VDC and 0.1 gram TDM successively, at room temperature stirred 0.5 hour, rotating speed 500～600rpm forms pre-emulsion.Then in another stainless steel cauldron, with 40.0 gram deionized waters, 0.2 gram 2A1 stirring and dissolving, logical nitrogen to reaction system pressure is 0.25MPa, be warmed up to 60 ℃ of solution that add 0.1 gram APS and 5.0 gram water as initial initiator, the pre-emulsion of adding 1/10 is as seed emulsion, question response system blueing light drips residue pre-emulsion and initiator simultaneously, and this initiator is the solution of 0.2 gram APS and 30.0 gram water.With dripping off pre-emulsion in 4 hours, with dripping off initiator in 4.5 hours.When pre-emulsion drips off, be warmed up to 86 ℃ of slakings 0.5 hour, cooling then, release, check, discharging.
Take by weighing quantitative polymer latex then, under agitation add quantitative dispersible pigment color paste, hydrogen peroxide, iron powder, hydrofluoric acid and deionized water at leisure, stirring to make the autodeposition coatings that is applicable to coated metal.The concrete prescription of autodeposition coatings sees Table 2.
Table 2
Claims (3)
1, a kind of vinylidene chloride-acrylate copolymer latex is characterized in that being obtained by the component reaction of following weight percentage:
(1) 1,1-Ethylene Dichloride 10～90%;
(2) the category-A reaction monomers 10～80%, and described category-A reaction monomers is one or more the mixture in methyl acrylate, ethyl propenoate, butyl acrylate, methyl methacrylate, vinyl cyanide, the methacrylonitrile;
(3) the category-B reaction monomers 1～10%, and described category-B reaction monomers is one or more the mixture in vinylformic acid, methacrylic acid, methylene-succinic acid, acrylamide, Methacrylamide, N hydroxymethyl acrylamide, hydroxyethyl methylacrylate, the Rocryl 410;
(4) esters of acrylic acid C monomer 0.5～5%, described esters of acrylic acid C monomer are glycidyl methacrylate or glytidyl methacrylate or its mixture;
(5) D class reaction monomers 0.5～5%, described D class reaction monomers are one or more the mixture in sodium vinyl sulfonate, allyloxy hydroxide sodium dimercaptosulphanatein, the hydroxyethyl methacrylate propanesulfonic acid sodium;
(6) emulsifying agent 0.5～5%, and described emulsifying agent is one or more the mixture in sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, alkyl diphenyl base oxide stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonate, ethoxylated alkylphenol ammonium sulfate, alkylphenol polyoxyethylene class, the sulfo-succinic acid disodium ethoxylated alcohol half ester;
(7) initiator 0.1～0.6%, and described initiator is Sodium Persulfate/sodium bisulfite, tertbutyl peroxide/sodium sulfoxylate formaldehyde/Fe
3+, tertbutyl peroxide/saccharosonic acid/Fe
3+, ammonium persulphate, Potassium Persulphate or Diisopropyl azodicarboxylate;
(8) the molecular chain transfer agent 0.1～0.5%, and described molecular chain transfer agent is tert-dodecyl mercaptan or 2 one mercaptoethanols or its mixture.
2, the preparation method of the described vinylidene chloride-acrylate copolymer latex of claim 1 is characterized in that comprising the steps:
(1) form pre-emulsion: with vinylidene chloride, category-A monomer, category-B monomer, esters of acrylic acid C monomer, D class monomer, emulsifying agent, molecular chain transfer agent and deionized water at room temperature, stirred 0.5 hour, rotating speed 500～600rpm produces pre-emulsion;
(2) seeded emulsion polymerization: in reactor, with deionized water, emulsifier for mixing dissolving, logical nitrogen to reaction system pressure is 0.25MPa, be warmed up to 60 ℃ and add the part initiator, the pre-emulsion of adding 1/10 is as seed emulsion, and question response system blueing light drips residue pre-emulsion and residue initiator simultaneously, with dripping off pre-emulsion in 4 hours, with dripping off initiator in 4.5 hours.
(3) slaking:, be warmed up to 86 ℃ of slakings 0.5 hour, cooling then, release, check, discharging when pre-emulsion and initiator drip off.
3, a kind of autodeposition coatings based on vinylidene chloride-acrylate copolymer latex is characterized in that comprising following component and weight percentage:
(1) the described vinylidene chloride-acrylate copolymer latex of claim 1;
(2) dispersible pigment color paste, weight are 1～20% of vinylidene chloride-acrylate copolymer latex;
(3) hydrogen peroxide of concentration 10%, weight are 0.5～10% of vinylidene chloride-acrylate copolymer latex;
(4) iron powder, weight are 0.1～5% of vinylidene chloride-acrylate copolymer latex;
(5) hydrofluoric acid of concentration 10%, weight are 0.5～15% of vinylidene chloride-acrylate copolymer latex.
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| CNB2007100273102A CN100497408C (en) | 2007-03-27 | 2007-03-27 | Self-deposition coating based on vinylidene chloride-acrylate copolymer latex and preparing method |
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| CNB2007100273102A CN100497408C (en) | 2007-03-27 | 2007-03-27 | Self-deposition coating based on vinylidene chloride-acrylate copolymer latex and preparing method |
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| CN100497408C true CN100497408C (en) | 2009-06-10 |
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| CN102250275B (en) * | 2011-06-07 | 2013-01-02 | 天津大学 | Method for preparing waterborne anticorrosion coating resin vinylidene chloride-acrylate |
| CN102250274B (en) * | 2011-06-07 | 2013-01-02 | 天津大学 | Method for preparing vinylidene chloride-acrylate emulsion |
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Assignee: MEILESHI PRINTING INK Co.,Ltd. Assignor: Sun Yat-sen University Contract record no.: 2011440001090 Denomination of invention: Self-deposition coating based on vinylidene chloride-acrylate copolymer latex and preparing method Granted publication date: 20090610 License type: Exclusive License Open date: 20070912 Record date: 20111220 |
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