CN1752166A - Process for preparing environment protection coating material by lacca modifying - Google Patents
Process for preparing environment protection coating material by lacca modifying Download PDFInfo
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- CN1752166A CN1752166A CN 200510086579 CN200510086579A CN1752166A CN 1752166 A CN1752166 A CN 1752166A CN 200510086579 CN200510086579 CN 200510086579 CN 200510086579 A CN200510086579 A CN 200510086579A CN 1752166 A CN1752166 A CN 1752166A
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Abstract
A process for preparing the environment protection type paint by lac modifying includes such steps as copolymerizing between natural lac and organic amine containing more than two aminos to obtain modified lac polymer, and mixing it with other polymer, slow-releasing agent and inorganic salt to obtain the paint with different components for wood, copper and its alloy, Al-Mg alloy, etc. Its advantages are high protecting and anticorrosion effect, high storage stability and no need of benzene solvent.
Description
Technical field
The invention belongs to the environment-protection coating material technical field, a kind of method of preparing environment protection coating material by lacca modifying particularly is provided.
Background technology
The protection of material and protection against corrosion are important topics of materials industry.The surface protection major requirement material of materials such as timber provides favorable mechanical performance, attractive in appearance etc., and the anticorrosion protection major requirement material of metallic substance is had the ability and the mechanical property of good anti-various environmental corrosions.Protection and anticorrosive commonly used at present mostly contain organic solvent, in construction and use environment and human body are caused bigger harm.Along with people to environment and healthy growing interest, and pollutent used and discharges supervision and strengthen, press for the novel environment protective antiseptic protection material that exploitation has excellent properties.
Shellac (Shellac) is formed a kind of natural moldable resin by insect secretory product.Have insulation, bonding, thermoplastic, waterproof, protection against the tide, antirust, corrosion resistant, characteristic such as nontoxic, be widely used in the industries such as military affairs, electric, coating, paint, machinery, rubber, plastics, process hides, papermaking, medicine, food.Invention number has been described by shellac, food wax, emulsifying agent etc. by a certain percentage for the patent of CN1137625, passes through processes such as heating, high-speed stirring, obtains fruit polishing and preserving treating agent.The patent of publication number 1067255 has been described and natural rubber is mixed with additive and has been made, and natural rubber is glue or the latex that solidifies, and additive is a diesel oil etc., and made tackiness agent has the ability of clinging insect, is applicable to that agricultural firing pest, family wipe out the flies and mosquitoes.The patent of publication number 1402805 has been described in the presence of an alkali metal salt of shellac, after nonionic hydrophilic monomer and hydrophobic monomer carried out polymerization, the mixing macromolecule dispersing agent prepares a kind of method of Surface Size, its purpose is that the mechanical stability of sizing agent itself and storage stability are good, good for acidic paper to the sizability of neutralized paper, and has the suitable property of good ink-jet with paper, particularly ink-jet with paper for information, and when the modulation coating fluid, the foaminess of this coating fluid significantly diminishes, and is good with other intermiscibility that share medicine.
Summary of the invention
The objective of the invention is to: the method that a kind of preparing environment protection coating material by lacca modifying is provided, promptly form the physical and mechanical properties that crosslinking structure improves shellac by chemical reaction, the thinner of going into sustained release dosage, inorganic salt and environmental sound prepares the method for environment friendly coated layer material.This material the construction and use in to environment and body harmless.
Shellac of the present invention comprises the starting material and the rough-wrought product thereof of lac, white lac (the white shellac of popular name) etc.
The present invention obtains the modification shellac polymer with natural shellac and the organic amine copolymerization that contains amino more than two; Concrete processing step is as follows:
A, stirring are dissolved in shellac in the thinner down, as not dissolving fully, can be heated to 50～80 ℃ till whole dissolvings under the room temperature, obtain the shellac solution of 10～50 weight %.Described thinner comprises: alcohols such as ethanol, butanols etc., ketone such as acetone, butanone, solvent such as non-benzene series thing such as ester class such as ethyl acetate, butylacetate etc.
B, get and be equivalent to the containing more than two in the solution that amino organic amine adds step a of shellac weight 1～10 weight %, reacted 1-4 hour warming while stirring to 45～80 ℃, obtains modification shellac solution, and the shellac solution that obtains can directly be used.The described organic amine that contains amino more than two comprises: thiocarbamide, second diamino, third diamino, fourth diamino, own diamino, divinyl triammonium, triethylene four ammonia, tetrem alkene five ammonia, the many ammonia of many ethene, Ursol D etc.
C, the liquid of step b carried out next step configuration at solution state; Or solvent evaporated obtains solid.Solid is diluted to the shellac solution use of 10～50 weight % before use with thinner.
Stir down and in concentration is the modification shellac solution of 10～50 weight %, to add the sustained release dosage that is equivalent to shellac weight 0.1～5 weight % and stirred 1-2 hour.Can also can solvent evaporated obtain solid (being mixed with the shellac solution of 10～50 weight % before the use) in the direct use of solution state.Described sustained release dosage uses for one or more heterogeneous ring compounds mix, and heterogeneous ring compound comprises: benzotriazole and derivative, 2-mercaptobenzothiazole and derivative, benzoglyoxaline and derivative, benzoxazole and derivative etc.
Stir down and in concentration is the modification shellac solution of 10～50 weight %, to add the sustained release dosage that is equivalent to shellac weight 0.1～5 weight % and stirred 1-2 hour.The inorganic salt that under agitation add 0.1～5 weight % then stirred 1-2 hour.This solution can directly use at solution state, also can solvent evaporated obtain solid.Described inorganic salt comprise molybdate, sulfonate, halogenide etc.
The application of coated material:
1). it is that the shellac solution of 10～50 weight % is by brushing or the method for spraying directly is coated on wood surface as priming paint or finish paint that the described solution of c or solid material are stirred compound concentration down with thinner.Following 5 minutes of this coating room temperature can surface drying, 24 hours complete dryinies, or realized complete dryinies down in dry 1 hour at 40～60 ℃ behind the surface drying.This coating has physical strength preferably, can effectively protect the surface of wood materials.
2). it is that the shellac solution of 10～50 weight % is by brushing or the method for spraying directly is coated on surfaces such as copper and alloy, aluminium and magnesium alloy as anti-corrosive protective material that the described solution of c or solid material are stirred compound concentration down with thinner.Following 5 minutes of this coating room temperature can surface drying, 24 hours complete dryinies, or realized complete dryinies down in dry 1～3 hour at 40～60 ℃ behind the surface drying.This coating has excellent mechanical intensity, has good Corrosion Protection simultaneously, can obviously improve the ability of non-ferrous metal and the anti-various environmental corrosions of alloy, is a kind of anticorrosion barrier material of excellent combination property.
3). this coated material does not discharge the volatile organic matter that country prohibites after constructing, deposit and using, be environment friendly coated layer material.
Basic mechanism of the present invention is that the multiple carboxyl reaction in multi-functional organic amine and the shellac forms amido linkage and reaches crosslinked purpose.The purpose that the mechanical property that the formation of cross-linked structure has improved shellac reaches material protection has improved simultaneously and has stoped the erosional competency of extraneous factor to the metallic surface; Amido linkage can improve the cohesive force at shellac and interface and to the resistance to corrosion of metallic substance.Adding sustained release dosage and inorganic salt etc. makes the Corrosion Protection of modification shellac that significantly raising be arranged further.
Polymkeric substance of the present invention, polymkeric substance add inorganic salt face with sustained release dosage or polymkeric substance with sustained release dosage and mix, and obtain the coated material of different components, are applied to non-ferrous metal surfaces such as timber, copper and alloy, aluminum magnesium alloy and have the favorable protection preservative effect.This material can solid or solution state store stable performance.Coating by this material preparation is thinner with non-benzene series thing solvent, belongs to environment friendly coated layer material.
Embodiment
Embodiment 1:2 gram shellac adds 15 milliliters of ethanol, stirs until whole dissolvings.The thiocarbamide that adds 0.02 gram is warmed up to 50 ℃ under stirring, and reacts 1 hour.Soltion viscosity slightly increases, color burn.With the solution cool to room temperature, obtaining viscosity is the brown liquid of 8 seconds (being coated with-4 glasss).This liquid directly is coated on the smooth plank by brushing, and room temperature was placed 24 hours, and obtaining thickness is 2 micron coatings.Coating hardness H, sticking power is greater than 1 grade.
Embodiment 2:10 gram shellac adds 15 milliliters of ethanol, is warmed up to 75 ℃ until whole dissolvings under stirring.The quadrol that adds 1 gram is warmed up to 50 ℃ under stirring, and reacts 4 hours.Soltion viscosity slightly increases, color burn.With the solution cool to room temperature, obtaining viscosity is the brown liquid of 15 seconds (being coated with-4 glasss).This liquid directly is coated on the smooth plank by brushing, and room temperature was placed 24 hours, obtained thickness and be 10 microns coating.Coating hardness H, sticking power is greater than 1 grade.
Embodiment 3:2 gram shellac adds 15 milliliters of ethanol, and stirring at room 2 hours is until whole dissolvings.The thiocarbamide that adds 0.02 gram is warmed up to 50 ℃ under stirring, and reacts 2 hours.Soltion viscosity slightly increases, color burn.With the solution cool to room temperature, obtaining viscosity is the brown liquid of 8 seconds (being coated with-4 glasss).This liquid directly is coated on the copper sheet of sand papering, washing with acetone after drying by brushing, and room temperature was placed 5 minutes, 50 ℃ dry 1 hour down, obtain thickness and be 2 microns coating.Coating hardness H, sticking power are greater than 1 grade, and the salt spray resistance experiment reaches 48 hours.
Embodiment 4:10 gram shellac adds 15 milliliters of butanone, is warmed up to 80 ℃ until whole dissolvings under stirring.The quadrol that adds 1 gram is warmed up to 50 ℃ under stirring, and reacts 2 hours.Soltion viscosity slightly increases, color burn.With the solution cool to room temperature, obtaining viscosity is the brown liquid of 15 seconds (being coated with-4 glasss).Add 0.02 in this liquid this liquid directly is coated on the copper sheet of sand papering, washing with acetone after drying by brushing, room temperature was placed 5 minutes, 50 ℃ dry 1 hour down, obtain thickness and be 10 microns coating.Coating hardness H, sticking power are greater than 1 grade, and the salt spray resistance experiment reaches 60 hours.
Embodiment 5; 10 gram shellac add 15 milliliters of butanone, are warmed up to 80 ℃ under stirring and stir 1 hour until whole dissolvings.The quadrol that adds 1 gram is warmed up to 50 ℃ under stirring, and reacts 3 hours.Soltion viscosity slightly increases, color burn.With the solution cool to room temperature, obtaining viscosity is the brown liquid of 15 seconds (being coated with-4 glasss).This liquid directly is coated on the aluminum magnesium alloy plate of the little AZ41M of the trade mark of sand papering, washing with acetone after drying by brushing, and room temperature was placed 5 minutes, 50 ℃ dry 1 hour down, obtain thickness and be 10 microns coating.Coating hardness H, sticking power are greater than 1 grade, and the salt spray resistance experiment reaches 30 hours.
Embodiment 6:10 gram shellac adds 15 milliliters of ethanol, is warmed up to 45 ℃ until whole dissolvings under stirring.The quadrol that adds 1 gram is warmed up to 50 ℃ under stirring, and reacts 4 hours.Soltion viscosity slightly increases, color burn.With the solution cool to room temperature, obtaining viscosity is the brown liquid of 15 seconds (being coated with-4 glasss).Add the benzotriazole of 0.1 gram in this solution, stirred 30 minutes, this liquid directly is coated on the copper sheet of sand papering, washing with acetone after drying by brushing, and room temperature was placed 5 minutes, and 50 ℃ of dryings 1 hour down obtain thickness and be 10 microns coating.Coating hardness H, sticking power are greater than 1 grade, and the salt spray resistance experiment reaches 72 hours.
Embodiment 7:10 gram shellac adds 15 milliliters of butanone, is warmed up to 80 ℃ until whole dissolvings under stirring.The quadrol that adds 1 gram is warmed up to 50 ℃ under stirring, and reacts 4 hours.Soltion viscosity slightly increases, color burn.With the solution cool to room temperature, obtaining viscosity is the brown liquid of 15 seconds (being coated with-4 glasss).Add the benzotriazole of 0.5 gram in this solution, stirred 30 minutes, this liquid directly is coated on the copper sheet of sand papering, washing with acetone after drying by brushing, and room temperature was placed 5 minutes, and 50 ℃ of dryings 1 hour down obtain thickness and be 10 microns coating.Coating hardness H, sticking power are greater than 1 grade, and the salt spray resistance experiment reaches 84 hours.
Embodiment 8:10 gram shellac adds 15 milliliters of ethanol, is warmed up to 45 ℃ until whole dissolvings under stirring.The quadrol that adds 1 gram is warmed up to 50 ℃ under stirring, and reacts 4 hours.Soltion viscosity slightly increases, color burn.With the solution cool to room temperature, obtaining viscosity is the brown liquid of 15 seconds (being coated with-4 glasss).Adding the benzotriazole of 0.5 gram and the molybdic acid of 0.5 gram in this solution receives, stirred 30 minutes, this liquid directly is coated on the copper sheet of sand papering, washing with acetone after drying by brushing, and room temperature was placed 5 minutes, 50 ℃ dry 1 hour down, obtain thickness and be 10 microns coating.Coating hardness H, sticking power are greater than 1 grade, and the salt spray resistance experiment reaches 96 hours.
Embodiment 9:2 gram shellac adds 15 milliliters of ethanol, stirs until whole dissolvings.The polyethylene polyamine that adds 0.002 gram is warmed up to 50 ℃ under stirring, and reacts 1 hour.Soltion viscosity slightly increases, color burn.With the solution cool to room temperature, obtaining viscosity is the brown liquid of 8 seconds (being coated with-4 glasss).In this solution, add the benzotriazole of 0.0025 gram and the potassiumiodide of 0.0025 gram, stirred 30 minutes, this liquid directly is coated on the copper sheet of sand papering, washing with acetone after drying by brushing, and room temperature was placed 5 minutes, 50 ℃ dry 1 hour down, obtain thickness and be 3 microns coating.Coating hardness H, sticking power are greater than 1 grade, and the salt spray resistance experiment reaches 60 hours.
Embodiment 10:10 gram shellac adds 15 milliliters of butanone, is warmed up to 80 ℃ under stirring and stirs 1 hour until whole dissolvings.The quadrol that adds 1 gram is warmed up to 50 ℃ under stirring, and reacts 2 hours.Soltion viscosity slightly increases, color burn.With the solution cool to room temperature, obtaining viscosity is the brown liquid of 15 seconds (being coated with-4 glasss).In this solution, add the benzotriazole of 0.25 gram and the di-mercaptobenzothiazolby of 0.25 gram, stirred 30 minutes, this liquid directly is coated on the copper sheet of sand papering, washing with acetone after drying by brushing, room temperature was placed 5 minutes, 50 ℃ dry 1 hour down, obtain thickness and be 10 microns coating.Coating hardness H, sticking power are greater than 1 grade, and the salt spray resistance experiment reaches 84 hours.
Claims (3)
1, a kind of method of preparing environment protection coating material by lacca modifying obtains the modification shellac polymer with natural shellac and the organic amine copolymerization that contains amino more than two; It is characterized in that: concrete processing step is as follows:
A, stirring are dissolved in shellac in the thinner down, and heating is till whole dissolvings, and Heating temperature is 50～80 ℃, obtains the shellac solution of 10～50 weight %; Described thinner comprises: alcohols such as ethanol, butanols etc., ketone such as acetone, butanone, solvent such as non-benzene series thing such as ester class such as ethyl acetate, butylacetate etc.;
B, get and be equivalent to the containing more than two in the solution that amino organic amine adds step a of shellac weight 1～10 weight %, reacted 1～4 hour warming while stirring to 45～80 ℃, obtains modification shellac solution, and the shellac solution that obtains is directly used; The described organic amine that contains amino more than two comprises: thiocarbamide, second diamino, third diamino, fourth diamino, own diamino, divinyl triammonium, triethylene four ammonia, tetrem alkene five ammonia, the many ammonia of many ethene, Ursol D;
C, the liquid of step b carried out next step configuration at solution state; Or solvent evaporated obtains solid.Solid is diluted to the shellac solution use of 10～50 weight % before use with thinner.
2, in accordance with the method for claim 1, it is characterized in that: stir down and in concentration is the modification shellac solution of 10～50 weight %, to add the sustained release dosage that is equivalent to shellac weight 0.1～5 weight % and stirred 1～2 hour; Obtain solid in direct use of solution state or solvent evaporated; Described sustained release dosage uses for one or more heterogeneous ring compounds mix, and heterogeneous ring compound comprises: benzotriazole and derivative, 2-mercaptobenzothiazole and derivative, benzoglyoxaline and derivative, benzoxazole and derivative.
3, in accordance with the method for claim 1, it is characterized in that: stir down and in concentration is the modification shellac solution of 10～50 weight %, to add the sustained release dosage that is equivalent to shellac weight 0.1～5 weight % and stirred 1～2 hour; Under agitation add the inorganic salt that are equivalent to shellac weight 0.1～5 weight % then and stirred 1～2 hour, this solution low-temperature evaporation falls solvent and obtains solid; Or directly use at solution state, described inorganic salt comprise molybdate, sulfonate, halogenide etc.
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| CNB2005100865799A CN100415840C (en) | 2005-10-10 | 2005-10-10 | Process for preparing environment protection coating material by lacca modifying |
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| CNB2005100865799A CN100415840C (en) | 2005-10-10 | 2005-10-10 | Process for preparing environment protection coating material by lacca modifying |
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| CN1752166A true CN1752166A (en) | 2006-03-29 |
| CN100415840C CN100415840C (en) | 2008-09-03 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104327730A (en) * | 2014-11-26 | 2015-02-04 | 江苏博腾新材料股份有限公司 | Durable insulating coating |
| CN105228825A (en) * | 2012-12-31 | 2016-01-06 | 查姆奈斯生物降解有限责任公司 | Moisture-resistant coating |
| CN110997843A (en) * | 2017-08-25 | 2020-04-10 | Ppg工业俄亥俄公司 | Metal can coated with shellac-containing coating |
| CN114790365A (en) * | 2021-01-26 | 2022-07-26 | 五峰赤诚生物科技股份有限公司 | Tannin/furfural-shellac resin anticorrosive paint and preparation method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1003218B (en) * | 1987-07-23 | 1989-02-08 | 陕西省金属结构厂 | Coating for core support and internal chill |
| CN1093968A (en) * | 1993-04-21 | 1994-10-26 | 何维光 | A kind of colouring liquor for woodenware and preparation technology thereof |
| CN1151219C (en) * | 2000-08-25 | 2004-05-26 | 韩京生 | Process for producing shellac paint |
| TW200424273A (en) * | 2002-11-14 | 2004-11-16 | Kansai Paint Co Ltd | Powder coating, method for production thereof, method for using the powder coating and coated article |
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2005
- 2005-10-10 CN CNB2005100865799A patent/CN100415840C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105228825A (en) * | 2012-12-31 | 2016-01-06 | 查姆奈斯生物降解有限责任公司 | Moisture-resistant coating |
| CN104327730A (en) * | 2014-11-26 | 2015-02-04 | 江苏博腾新材料股份有限公司 | Durable insulating coating |
| CN110997843A (en) * | 2017-08-25 | 2020-04-10 | Ppg工业俄亥俄公司 | Metal can coated with shellac-containing coating |
| CN114790365A (en) * | 2021-01-26 | 2022-07-26 | 五峰赤诚生物科技股份有限公司 | Tannin/furfural-shellac resin anticorrosive paint and preparation method thereof |
| CN114790365B (en) * | 2021-01-26 | 2023-01-31 | 五峰赤诚生物科技股份有限公司 | Tannin/furfural-shellac resin anticorrosive paint and preparation method thereof |
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| CN100415840C (en) | 2008-09-03 |
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