CN101580653A - Organic-inorganic hybrid nanometer film coating aluminum powder pigment and preparation method and application thereof - Google Patents
Organic-inorganic hybrid nanometer film coating aluminum powder pigment and preparation method and application thereof Download PDFInfo
- Publication number
- CN101580653A CN101580653A CNA2009100401627A CN200910040162A CN101580653A CN 101580653 A CN101580653 A CN 101580653A CN A2009100401627 A CNA2009100401627 A CN A2009100401627A CN 200910040162 A CN200910040162 A CN 200910040162A CN 101580653 A CN101580653 A CN 101580653A
- Authority
- CN
- China
- Prior art keywords
- parts
- powder pigment
- aluminum powder
- organic
- carbon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses organic-inorganic hybrid nanometer film coating aluminum powder pigment and a preparation method and application thereof. The preparation method comprises the followings steps: by utilizing organic-inorganic hybrid technology and taking aluminum powder pigment as nuclear, firstly performing free radical polymerization on polymerisable carbon-carbon double bond reaction monomers and polymerisable carbon-carbon double bond organosiloxane; and bonding the obtained polymer and ethyl orthosilicate with the surface of the aluminum powder pigment in a hydrolysis mode, and further coating a layer of organic-inorganic hybrid nanometer film on the surface of the aluminum powder. On the basis of maintaining the lustrousness of the aluminum powder, the prepared organic-inorganic hybrid nanometer film coating aluminum powder pigment has excellent compatibility with resin and good acid and alkaline resistance properties, simultaneously well solves the problem of 'powder falling' when the conventional aluminum powder and single-layer or two-layer costing aluminum powder pigment are applied to metallic coatings, and provides a foundation for applying modified aluminum powder pigment and developing high performance metallic coatings.
Description
Technical field
The present invention relates to the organic inorganic hybridization technical field, specifically be meant a kind of organic-inorganic hybrid nanometer film coating aluminum powder pigment and utilisation technology method thereof.
Background technology
In recent years, along with the lifting in field demands such as covering with paint, decorations of aluminium-silver slurry, protective coating, aluminium powder pigment has obtained paying close attention to widely.Glossiness height, strong adhesion, the corrosion-resistant key that has become to weigh aluminium powder pigment performance height.In order to obtain above-mentioned high performance pigments, need carry out modification to the aluminium powder surface and handle.Method commonly used at present all is based on the chemoproection method, mainly is divided into additive method and coating method.Additive method promptly on the surface of aluminium granules of pigments with the physical method mixed additive, at protective layer of the outer formation of aluminium flake, as in aluminium paint, adding additive passivation aluminium powder surfaces such as phosphoric acid, molybdic acid, but adsorptive power is not strong, additive is easy to come off, finally cause modified aluminium powder pigment corrosion-resistant not lasting, thereby additive is limited to the provide protection of aluminium powder pigment; The coating method is the material that deposits or coat unit molecule or polymolecular layer on the pigment particles surface, comprise inorganic oxide or high molecular polymer, to increase particle surface polarity, make it to improve with the consistency of the resin or the aqueous solution, assemble thereby reduce pigment particles, improve performances such as wettability, dispersiveness, homogeneity.In addition, because coating layer is transparency material, can keep the distinctive gloss of aluminium powder pigment preferably, therefore, in the research of modified aluminium powder pigment, the coating method is the most effective and the method for worth further investigation.
Divide from coating layer, aluminium powder coats and is divided into individual layer coating and double-coated two classes.Individual layer coats and mainly refers to the coupling agent treatment modification.Silane coupling agent is the coupling agent that generally uses, and when carrying out coupling processing, oxyalkyl is hydrolyzed into hydroxyl, and then shrinks with the hydroxyl on aluminium powder surface and to form alumina silicon key, promptly coats the silicon dioxide film of one deck densification on the aluminium powder surface.This method has good anticorrosive effect to aluminium pigment, but is a big defective in present coupling agent treatment method of modifying with the consistency of filmogen with the aluminium pigment applications of coupling agent treatment modification in coating; Double-coated is mainly based on the preparation method of Chinese patent 200610123751.8 disclosed a kind of coated aluminium powder pigments.This method is to add polymerisable monomer on the basis that individual layer coats, and promptly is nuclear with the aluminium powder pigment, and organo-siloxane at first forms the first layer coating layer on the aluminium powder pigment surface, and polymkeric substance forms second layer coating layer on the aluminium powder pigment surface then.The modified aluminium powder of this kind method preparation and the consistency of filmogen have some improvement, but have the problem that coating layer is inhomogeneous, the film forming tack is not strong, reaction process is reunited easily.
Hybrid inorganic-organic is by the network structure that constitutes skeleton between inorganic and organism on one dimension direction at least by the chemical bonding effect jointly.The hybrid organic-inorganic film of high-sequential has overcome the defective on coating of aluminium powder individual layer and the double-coated performance, and organic coating and functional inorganic substance complementary performance combined, promptly hybridized film than individual layer or the densification of duplicature homogeneous, smooth, the antioxidant anticorrosive performance is good, glossiness is high.In pigment applications, organic inorganic hybridization film metallized aluminum pigment coating adhesion can be good simultaneously.At present, still find no the machine inorganic hybridization both at home and abroad and make up the report that nanometer film coats aluminium powder pigment, this patent utilizes the organic inorganic hybridization method to prepare the organic-inorganic hybrid nanometer film coating aluminum powder particle, promptly at first synthetic carbon-carbon double bond class organosiloxane polymer, utilize carbon-carbon double bond class organosiloxane polymer and tetraethoxy generation synergetic hydrolysis to form hybrid organic-inorganic film again, utilize hybridized film to improve antiseptic property and glossiness, utilize the organism segment of polymkeric substance to improve the film forming tack.Adopt the organic inorganic hybridization technology, both can improve the dispersed of aluminium powder pigment and with the performance such as compatible of resin, keep the original glossiness of aluminium powder pigment, the practicality of aluminium powder pigment is improved, and be expected to obtain the nanometer film coating material in the synergy that comprises on the multiple function of preservative efficacy.
Summary of the invention
The objective of the invention is in order to solve the deficiency that prior art exists, a kind of high film forming sticking power, good corrosion resistance, organic-inorganic hybrid nanometer film coating aluminum powder pigment that glossiness is high and preparation method thereof are provided.
Another object of the present invention is to provide and use the application that organic-inorganic hybrid nanometer film coating aluminum powder pigment aluminium powder pigment is filmed in preparation, this coating film gloss degree is good, good with organism consistency such as resin, acid and alkali-resistance is good, coating adhesion is high.
Purpose of the present invention is achieved through the following technical solutions:
The preparation method of organic-inorganic hybrid nanometer film coating aluminum powder pigment comprises the steps and processing condition:
The first step is in mass fraction, under nitrogen protection, in first reaction vessel, add 1～10 part of carbon-carbon double bond class organo-siloxane, 1～10 part one or more contain the polymerisable monomer of carbon-carbon double bond class, 40-60 part solvent, 0.01～3 part of initiator, temperature of reaction is 60～110 ℃, reacted 2～10 hours, carry out radical polymerization, obtain carbon-carbon double bond class organosiloxane polymer, the number-average molecular weight of described carbon-carbon double bond class organosiloxane polymer is 300～100000; Described carbon-carbon double bond class organo-siloxane is R ' (CH
2) nSi (OR)
3Or R ' (CH
2) n Si (OR)
2(R "), wherein, n=0,1,2 or 3, OR are hydrolyzable alkoxyl group, R ' for have the carbon-carbon double bond class can with organic segment of the polymerisable monomer copolymerization generation copolymerization of carbon-carbon double bond class, R " is methyl or ethyl; Described solvent is toluene, dimethylbenzene or butylacetate; Described initiator is benzoyl peroxide or Diisopropyl azodicarboxylate;
Second step added 2～10 parts of aluminium powder pigments and 30～60 parts of alcoholic solvents in mass fraction in second reaction vessel, stirred under the room temperature 0.5～2 hour; Described alcoholic solvent is methyl alcohol, ethanol, propyl alcohol or Virahol; Described aluminium powder pigment is laminar, the long and wide 100nm～50 μ m that are respectively, and thickness is 10～40nm;
The 3rd step added 20～40 parts of described carbon-carbon double bond class of the first step organosiloxane polymers, 2～8 parts of tetraethoxys, 4～15 parts of water, 2～8 parts of ammoniacal liquor and 10～30 parts of alcoholic solvents in described second reaction vessel of second step, temperature of reaction is 30～60 ℃, reacted 2～10 hours, filter, washing, drying at room temperature obtains organic-inorganic hybrid nanometer film coating aluminum powder pigment; Described alcoholic solvent is methyl alcohol, ethanol, propyl alcohol or Virahol.
The described organic segment that has the carbon-carbon double bond class is butadienyl, vinyl, methacryloxy or propenyl.
Described hydrolyzable alkoxyl group is methoxyl group, oxyethyl group or acetoxyl group.
Described carbon-carbon double bond class organo-siloxane is vinyltrimethoxy silane, vinyltriethoxysilane, vinyltriacetoxy silane, butadienyl triethoxyl silane or γ-methacryloxypropyl trimethoxy silane.
The described polymerisable monomer that contains the carbon-carbon double bond class is vinylbenzene, Vinylstyrene, (methyl) methyl acrylate, (methyl) butyl acrylate, vinylformic acid, methacrylic acid, maleic anhydride or norbornene dicarboxylic anhydride.
The organic-inorganic hybrid nanometer film coating aluminum powder pigment of method for preparing: with the aluminium powder pigment is nuclear, carbon-carbon double bond class organosiloxane polymer and tetraethoxy coat one deck organic-inorganic hybrid nanometer film by the mode of synergetic hydrolysis on the aluminium powder pigment surface, hybrid nanometer film combines with the Si-O-Al chemical bond with the aluminium powder pigment surface, and hybrid nanometer film inside-Si-O-is interweaved into network structure with organic chain on three-dimensional space.
The application of described organic-inorganic hybrid nanometer film coating aluminum powder pigment: 2～6 parts of organic-inorganic hybrid nanometer film coating aluminum powder pigment, 5～30 parts of thermoplastic acrylic resins, 30～80 parts of solvents are at room temperature mixed, on metal or aluminium-plastic panel ground, spray, obtain flash type and film; Described solvent is toluene, dimethylbenzene or butylacetate.
Organic-inorganic hybrid nanometer film coating aluminum powder pigment soaks nondiscoloration in 30 days in the acidic solution of pH=1, soak nondiscoloration in 180 days in the basic solution of pH=9, soaks nondiscoloration in 30 days in the pH=11 basic solution; Organic-inorganic hybrid nanometer film coating aluminum powder pigment is filmed, and its surface gloss is 96～100% of aluminium powder pigment film coated surface glossiness before coating, adheres to through the extraordinary adhesive tape of NICHIBAN, and the aluminium powder amount of coming off is lower than 3%.
The present invention compared with prior art has following advantage and beneficial effect:
1. the present invention is in preparation process, at first adopt carbon-carbon double bond class polymerisable monomer and carbon-carbon double bond class organo-siloxane to carry out Raolical polymerizable and obtain carbon-carbon double bond class organosiloxane polymer, utilize the synergetic hydrolysis condensation reaction of this polymkeric substance and tetraethoxy that the aluminium powder pigment particle is carried out the organic-inorganic hybrid nanometer film coating again.
2. organic-inorganic hybrid nanometer film densification, handle aluminium powder pigment, individual layer and double-coated aluminium powder pigment with respect to physical absorbent, can effectively completely cut off aluminium powder pigment and other corrosive mediums,, have acid and alkali-resistance and water tolerance preferably as the contact of oxygen, water, acid and alkali.
3. organic-inorganic hybrid nanometer film coating aluminum powder pigment is with respect to individual layer silicon dioxide coating type aluminium powder pigment, and hybrid nanometer film is smooth transparent, makes coated aluminium powder pigment have preferred metal gloss.
4. the prepared organic-inorganic hybrid nanometer film coating aluminum powder pigment of the present invention is with respect to the polymer overmold type aluminium powder pigment of in-situ polymerization or emulsion polymerization prepared, can be by control radical polymerization process control carbon-carbon double bond organic segmental length of class organosiloxane polymer and polarity, thereby significantly improve the consistency of hybridized film and resin system and the film forming tack of coating aluminium powder pigment, reach the not requirement of dry linting of filming.
Embodiment
Below in conjunction with embodiment, the present invention is described further, embodiments of the invention are not limit so.Umber among the following embodiment all is a mass fraction.
Embodiment 1-6 is the preparation method of organic-inorganic hybrid nanometer film coating aluminum powder pigment
Embodiment 1
The first step adds 5 parts of vinyltrimethoxy silanes in first reaction vessel under nitrogen protection, 6 parts of vinylbenzene, 40 parts of butylacetates, 1 part of Diisopropyl azodicarboxylate, stir reaction down 10 hours, temperature of reaction is 60 ℃, obtains the polymkeric substance of carbon-carbon double bond class organo-siloxane and carbon-carbon double bond class polymerisable monomer;
Second step added 2 parts of aluminium powder pigments and 40 parts of methyl alcohol in mass fraction in second reaction vessel, stirred 0.5 hour under the room temperature; Aluminium powder pigment is laminar, the long and wide 100nm～50 μ m that are respectively, and thickness is 10～40nm;
The 3rd step added 20 parts of polymkeric substance, the mixture of 5 parts of tetraethoxys, 4 parts of water, 2 parts of ammoniacal liquor and 10 parts of alcoholic acid mixtures of the first step gained in described second reaction vessel of second step, wherein the mixture of 20 of the first step gained parts of polymkeric substance and 5 parts of tetraethoxys and 4 parts of water, 2 parts of ammoniacal liquor and 10 parts of alcoholic acid mixtures drip simultaneously with 1 droplet/second speed, stir reaction down 4 hours, temperature of reaction is 30 ℃; Aluminium powder pigment suspension is cooled to room temperature, filters, filter residue is used ethanol, three after-filtration of distilled water wash successively, drying at room temperature, be 4 hours time of drying, obtains organic-inorganic hybrid nanometer film coating aluminum powder pigment;
Coated aluminium powder pigment, 4 parts of butylacetates, 18 parts of thermoplastic acrylic resins, 50 parts of toluene that the 4th step obtained 4 part of the 3rd step at room temperature mix, and the spraying spraying obtains flash type and films on the aluminium-plastic panel ground.
Embodiment 2
The first step is in mass fraction, under nitrogen protection, in first reaction vessel, add 3 parts of butadienyl triethoxyl silanes, 6 parts of butyl methacrylate, 40 parts of dimethylbenzene, 0.5 part benzoyl peroxide, stir reaction down 6 hours, temperature of reaction is 110 ℃, obtains the polymkeric substance of carbon-carbon double bond class organo-siloxane and carbon-carbon double bond class polymerisable monomer;
Second step added 4 parts of aluminium powder pigments and 40 parts of propyl alcohol in mass fraction in second reaction vessel, stirred 1 hour under the room temperature; Aluminium powder pigment is laminar, the long and wide 100nm～50 μ m that are respectively, and thickness is 10～40nm;
The 3rd step added 40 parts of polymkeric substance, the mixture of 5 parts of tetraethoxys, 6 parts of water, 3 parts of ammoniacal liquor and 10 parts of alcoholic acid mixtures of the first step gained in described second reaction vessel of second step, wherein the mixture of 40 of the first step gained parts of polymkeric substance and 5 parts of tetraethoxys and 6 parts of water, 3 parts of ammoniacal liquor and 10 parts of alcoholic acid mixtures drip simultaneously with 1 droplet/second speed, stir reaction down 6 hours, temperature of reaction is 50 ℃; Aluminium powder pigment suspension is cooled to room temperature, filters, filter residue is used ethanol, three after-filtration of distilled water wash successively, drying at room temperature, be 4 hours time of drying, obtains organic-inorganic hybrid nanometer film coating aluminum powder pigment;
Coated aluminium powder pigment, 4 parts of butylacetates, 15 parts of thermoplastic acrylic resins, 50 parts of dimethylbenzene that the 4th step obtained 3 part of the 3rd step at room temperature mix, and spray on the aluminium-plastic panel ground, obtain flash type and film.
Embodiment 3
The first step is in mass fraction, under nitrogen protection, in first reaction vessel, add 8 parts of vinyltriacetoxy silanes, 9 parts of methyl methacrylates, 60 parts of toluene, 1 part of Diisopropyl azodicarboxylate, stir reaction down 2 hours, temperature of reaction is 90 ℃, obtains the polymkeric substance of carbon-carbon double bond class organo-siloxane and carbon-carbon double bond class polymerisable monomer;
Second step added 4 parts of aluminium powder pigments and 60 parts of ethanol in mass fraction in second reaction vessel, stirred 2 hours under the room temperature; Aluminium powder pigment is laminar, the long and wide 100nm～50 μ m that are respectively, and thickness is 10～40nm;
The 3rd step added 40 parts of polymkeric substance, the mixture of 8 parts of tetraethoxys, 12 parts of water, 8 parts of ammoniacal liquor and 20 parts of alcoholic acid mixtures of the first step gained in described second reaction vessel of second step, wherein the mixture of 40 of the first step gained parts of polymkeric substance and 8 parts of tetraethoxys and 15 parts of water, 6 parts of ammoniacal liquor and 20 parts of alcoholic acid mixtures drip simultaneously with 1 droplet/second speed, stir reaction down 10 hours, temperature of reaction is 60 ℃; Aluminium powder pigment suspension is cooled to room temperature, filters, filter residue is used ethanol, three after-filtration of distilled water wash successively, drying at room temperature, be 8 hours time of drying, obtains organic-inorganic hybrid nanometer film coating aluminum powder pigment;
Coated aluminium powder pigment, 8 parts of butylacetates, 18 parts of thermoplastic acrylic resins, 50 parts of toluene that the 4th step obtained 6 part of the 3rd step at room temperature mix, and spray on the aluminium-plastic panel ground, obtain flash type and film.
Embodiment 4
The first step is in mass fraction, under nitrogen protection, in first reaction vessel, add 3 parts of vinyl three ethoxy silane, 3 parts of methyl acrylates, 60 parts of dimethylbenzene, 0.03 part Diisopropyl azodicarboxylate, stir reaction down 4 hours, temperature of reaction is 95 ℃, obtains the polymkeric substance of carbon-carbon double bond class organo-siloxane and carbon-carbon double bond class polymerisable monomer;
Second step added 1.5 parts of aluminium powder pigments and 50 parts of Virahols in mass fraction in second reaction vessel, stirred 0.5 hour under the room temperature; Aluminium powder pigment is laminar, the long and wide 100nm～50 μ m that are respectively, and thickness is 10～40nm;
The 3rd step added 20 parts of polymkeric substance, the mixture of 2 parts of tetraethoxys, 5 parts of water, 3 parts of ammoniacal liquor and 20 parts of alcoholic acid mixtures of the first step gained in described second reaction vessel of second step, wherein the mixture of 20 of the first step gained parts of polymkeric substance and 2 parts of tetraethoxys and 5 parts of water, 3 parts of ammoniacal liquor and 20 parts of alcoholic acid mixtures drip simultaneously with 1 droplet/second speed, stir reaction down 2 hours, temperature of reaction is 50 ℃; Aluminium powder pigment suspension is cooled to room temperature, filters, filter residue is used ethanol, three after-filtration of distilled water wash successively, drying at room temperature, be 4 hours time of drying, obtains organic-inorganic hybrid nanometer film coating aluminum powder pigment;
Coated aluminium powder pigment, 4 parts of butylacetates, 6 parts of thermoplastic acrylic resins, 35 parts of toluene that the 4th step obtained 2 part of the 3rd step at room temperature mix, and spray on the aluminium-plastic panel ground, obtain flash type and film.
Embodiment 5
The first step is in mass fraction, under nitrogen protection, in first reaction vessel, add 5 parts of γ-methacryloxypropyl trimethoxy silane, 3 parts of Vinylstyrenes, 50 parts of toluene, 0.5 part Diisopropyl azodicarboxylate, stir reaction down 6 hours, temperature of reaction is 85 ℃, obtains the polymkeric substance of carbon-carbon double bond class organo-siloxane and carbon-carbon double bond class polymerisable monomer;
Second step added 3 parts of aluminium powder pigments and 50 parts of ethanol in mass fraction in second reaction vessel, stirred 1 hour under the room temperature; Aluminium powder pigment is laminar, the long and wide 100nm～50 μ m that are respectively, and thickness is 10～40nm;
The 3rd step added 30 parts of polymkeric substance, the mixture of 5 parts of tetraethoxys, 9 parts of water, 4 parts of ammoniacal liquor and 30 parts of alcoholic acid mixtures of the first step gained in described second reaction vessel of second step, wherein the mixture of 30 of the first step gained parts of polymkeric substance and 5 parts of tetraethoxys and 9 parts of water, 4 parts of ammoniacal liquor and 30 parts of alcoholic acid mixtures drip simultaneously with 1 droplet/second speed, stir reaction down 8 hours, temperature of reaction is 55 ℃; Aluminium powder pigment suspension is cooled to room temperature, filters, filter residue is used ethanol, three after-filtration of distilled water wash successively, drying at room temperature, be 6 hours time of drying, obtains organic-inorganic hybrid nanometer film coating aluminum powder pigment;
Coated aluminium powder pigment, 5 parts of butylacetates, 8 parts of thermoplastic acrylic resins, 30 parts of dimethylbenzene that the 4th step obtained 3 part of the 3rd step at room temperature mix, and spray on the aluminium-plastic panel ground, obtain flash type and film.
Embodiment 6
The first step is in mass fraction, under nitrogen protection, in first reaction vessel, add 4 parts of vinyltriacetoxy silanes, 4 parts of maleic anhydrides, 40 parts of dimethylbenzene, 0.25 part benzoyl peroxide, stir reaction down 8 hours, temperature of reaction is 100 ℃, obtains the polymkeric substance of carbon-carbon double bond class organo-siloxane and carbon-carbon double bond class polymerisable monomer;
Second step added 3 parts of aluminium powder pigments and 60 parts of ethanol in mass fraction in second reaction vessel, stirred 0.5 hour under the room temperature; Aluminium powder pigment is laminar, the long and wide 100nm～50 μ m that are respectively, and thickness is 10～40nm;
The 3rd step added 30 parts of polymkeric substance, the mixture of 3.5 parts of tetraethoxys, 10 parts of water, 6 parts of ammoniacal liquor and 30 parts of alcoholic acid mixtures of the first step gained in described second reaction vessel of second step, wherein the mixture of 30 of the first step gained parts of polymkeric substance and 3.5 parts of tetraethoxys and 10 parts of water, 6 parts of ammoniacal liquor and 30 parts of alcoholic acid mixtures drip simultaneously with 1 droplet/second speed, stir reaction down 5 hours, temperature of reaction is 55 ℃; Aluminium powder pigment suspension is cooled to room temperature, filters, filter residue is used ethanol, three after-filtration of distilled water wash successively, drying at room temperature, be 7 hours time of drying, obtains organic-inorganic hybrid nanometer film coating aluminum powder pigment;
Coated aluminium powder pigment, 6 parts of butylacetates, 20 parts of thermoplastic acrylic resins, 60 parts of dimethylbenzene that the 4th step obtained 5 part of the 3rd step at room temperature mix, and spray on the aluminium-plastic panel ground, obtain flash type and film.
Embodiment 7
The aluminium powder pigment that organic-inorganic hybrid nanometer film coating aluminum powder pigment of the present invention and existing market are sold carries out alkali resistance relatively, the result is: the nanometer film coating aluminum powder pigment of embodiment 1～6 preparation is in the sodium hydroxide solution of pH=9, when room temperature is six months following storage period, all do not have hydrogen to produce, the color of pigment does not all change; And the aluminium powder pigment that sell in market (as the emerging ZC905 of family, ZC906) is in the sodium hydroxide solution of pH=9, and room temperature is promptly to have a large amount of hydrogen to emit in 15 days following storage period, and the color of pigment gradually becomes canescence.Prove that nanometer film coating aluminum powder pigment of the present invention has alkali resistance preferably in the sodium hydroxide solution of pH=9, and package stability is also better.In addition, illustrate that also the hydridization coating layer on nanometer film coating aluminum powder pigment of the present invention surface is dense, aluminium powder pigment is played the better protecting effect.
Embodiment 8
The aluminium powder pigment that organic-inorganic hybrid nanometer film coating aluminum powder pigment of the present invention and existing market are sold carries out alkali resistance relatively, the result is: the nanometer film coating aluminum powder pigment of embodiment 1～6 preparation is in the sodium hydroxide solution of pH=11, when room temperature is one month following storage period, all do not have hydrogen to produce, the color of pigment does not all change; And the aluminium powder pigment that sell in market (the emerging ZC905 of family, ZC906) is in the sodium hydroxide solution of pH=11, and room temperature is promptly to have a large amount of hydrogen to emit in 7 days following storage period, and the color of pigment gradually becomes canescence.Prove that nanometer film coating aluminum powder pigment of the present invention has alkali resistance preferably in the sodium hydroxide solution of pH=11, and package stability is also better.
Embodiment 9
The aluminium powder pigment that organic-inorganic hybrid nanometer film coating aluminum powder pigment of the present invention and existing market are sold carries out acid resistance relatively, the result is: the nanometer film coating aluminum powder pigment of embodiment 1～6 preparation is in the sulphuric acid soln of pH=1, when room temperature is one month following storage period, all do not have hydrogen to produce, the color of pigment does not all change; And the aluminium powder pigment that sell in market (the emerging ZC905 of family, ZC906) is in the sulphuric acid soln of pH=1, and room temperature is promptly to have a large amount of hydrogen to emit in 5 days following storage period, and the color of pigment gradually becomes canescence.Prove that nanometer film coating aluminum powder pigment of the present invention has acid resistance preferably in the sulphuric acid soln of pH=1, and package stability is also better.
Embodiment 10
Reference examples 1: 5 parts of aluminium powder raw material, 6 parts of butylacetates, 20 parts of thermoplastic acrylic resins, 60 parts of dimethylbenzene that do not coat are at room temperature mixed, on the aluminium-plastic panel ground, spray, obtain flash type and film.
Reference examples 2: coated aluminium powder pigment (the emerging ZC905 of family), 6 parts of butylacetates, 20 parts of thermoplastic acrylic resins, 60 parts of dimethylbenzene that 5 parts of markets are sold at room temperature mix, and spray on the aluminium-plastic panel ground, obtain flash type and film.
Reference examples 3: coated aluminium powder pigment (the emerging ZC906 of family), 6 parts of butylacetates, 20 parts of thermoplastic acrylic resins, 60 parts of dimethylbenzene that 5 parts of markets are sold at room temperature mix, and spray on the aluminium-plastic panel ground, obtain flash type and film.
With above reference examples 1, reference examples 2,3 is filmed with the coated aluminium powder pigment of embodiment 1～6 preparation respectively and is carried out following contrast test:
Glossiness test: organic-inorganic hybrid nanometer film coating aluminum powder pigment of the present invention filmed and coat before the aluminium powder raw material film and carry out the contrast of glossiness, with vancometer the product of reference examples 1 and embodiment 1～6 preparation is carried out the glossiness test;
Sticking power test: the aluminium powder pigment that organic-inorganic hybrid nanometer film coating aluminum powder pigment of the present invention and existing market are sold is applied in the coating contrast with filmogen sticking power, the product of reference examples 2,3 and embodiment 1～6 preparation is carried out the adhesive tape sticking experiment, adopt the adhesive tape method, being about to the extraordinary adhesive tape of NICHIBAN is attached to paint film and draws filming that the lattice device makes and draw on the lattice, tear with minimum angles then, the result tries to achieve according to the come off ratio of area of film coated surface.
The film performance test of the dissimilar aluminium pigment applications of table 1 in coating
The glossiness test result shows that organic-inorganic hybrid nanometer film coating aluminum powder pigment of the present invention films to 96%～100% of the aluminium powder pigment coating film gloss degree before coating, proves the glossiness that organic-inorganic hybrid nanometer film coating aluminum powder pigment of the present invention is filmed and can well be kept original aluminium powder raw material to film; The adhesive tape method is surveyed adhesion results and is shown, the aluminium powder amount of coming off was lower than 3% during organic-inorganic hybrid nanometer film coating aluminum powder pigment was filmed, and the amount of coming off of aluminium powder pigment that sell in market (the emerging ZC905 of family, ZC906) is about 30%, proves that organic-inorganic hybrid nanometer film coating aluminum powder pigment applications of the present invention has strong sticking power in coating.
Claims (7)
1, the preparation method of organic-inorganic hybrid nanometer film coating aluminum powder pigment is characterized in that comprising the steps and processing condition:
The first step is in mass fraction, under nitrogen protection, in first reaction vessel, add 1～10 part of carbon-carbon double bond class organo-siloxane, 1～10 part one or more contain the polymerisable monomer of carbon-carbon double bond class, 40-60 part solvent, 0.01～3 part of initiator, temperature of reaction is 60～110 ℃, reacted 2～10 hours, carry out radical polymerization, obtain carbon-carbon double bond class organosiloxane polymer, the number-average molecular weight of described carbon-carbon double bond class organosiloxane polymer is 300～100000; Described carbon-carbon double bond class organo-siloxane is R ' (CH
2) nSi (OR)
3Or R ' (CH
2) n Si (OR)
2(OR is hydrolyzable alkoxyl group for R "), n=0,1,2 or 3 wherein, and R ' is for having organic segment of carbon-carbon double bond class, and R " is methyl or ethyl; Described solvent is toluene, dimethylbenzene or butylacetate; Described initiator is benzoyl peroxide or Diisopropyl azodicarboxylate;
Second step added 2～10 parts of aluminium powder pigments and 30～60 parts of alcoholic solvents in mass fraction in second reaction vessel, stirred under the room temperature 0.5～2 hour; Described alcoholic solvent is methyl alcohol, ethanol, propyl alcohol or Virahol; Described aluminium powder pigment is laminar, the long or wide 100nm～50 μ m that are respectively, and thickness is 10～40nm.
The 3rd step added 20～40 parts of described carbon-carbon double bond class of the first step organosiloxane polymers, 2～8 parts of tetraethoxys, 4～15 parts of water, 2～8 parts of ammoniacal liquor and 10～30 parts of alcoholic solvents in described second reaction vessel of second step, temperature of reaction is 30～60 ℃, reacted 2～10 hours, filter, washing, drying at room temperature obtains organic-inorganic hybrid nanometer film coating aluminum powder pigment; Described alcoholic solvent is methyl alcohol, ethanol, propyl alcohol or Virahol.
2, according to the preparation method of the described organic-inorganic hybrid nanometer film coating aluminum powder pigment of claim 1, it is characterized in that: the described organic segment that has the carbon-carbon double bond class is butadienyl, vinyl, methacryloxy or propenyl.
3, according to the preparation method of the described organic-inorganic hybrid nanometer film coating aluminum powder pigment of claim 1, it is characterized in that: described hydrolyzable alkoxyl group is methoxyl group, oxyethyl group or acetoxyl group.
4, according to the preparation method of the described organic-inorganic hybrid nanometer film coating aluminum powder pigment of claim 1, it is characterized in that: described carbon-carbon double bond class organo-siloxane is vinyltrimethoxy silane, vinyltriethoxysilane, vinyltriacetoxy silane, butadienyl triethoxyl silane or γ-methacryloxypropyl trimethoxy silane.
5, according to the preparation method of the described organic-inorganic hybrid nanometer film coating aluminum powder pigment of claim 1, it is characterized in that: the described polymerisable monomer that contains the carbon-carbon double bond class is vinylbenzene, Vinylstyrene, (methyl) methyl acrylate, (methyl) butyl acrylate, vinylformic acid, methacrylic acid, maleic anhydride or norbornene dicarboxylic anhydride.
6, the organic-inorganic hybrid nanometer film coating aluminum powder pigment of the described method preparation of claim 1, it is characterized in that: be nuclear with the aluminium powder pigment, carbon-carbon double bond class organosiloxane polymer and tetraethoxy coat one deck organic-inorganic hybrid nanometer film by the mode of synergetic hydrolysis on the aluminium powder pigment surface, hybrid nanometer film combines with the Si-O-Al chemical bond with the aluminium powder pigment surface, and hybrid nanometer film inside-Si-O-is interweaved into network structure with organic chain on three-dimensional space.
7. the application of the described organic-inorganic hybrid nanometer film coating aluminum powder pigment of claim 6, it is characterized in that: 2～6 parts of organic-inorganic hybrid nanometer film coating aluminum powder pigment, 5～30 parts of thermoplastic acrylic resins, 30～80 parts of solvents are at room temperature mixed, on metal or aluminium-plastic panel ground, spray, obtain flash type and film; Described solvent is toluene, dimethylbenzene or butylacetate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100401627A CN101580653B (en) | 2009-06-10 | 2009-06-10 | Organic-inorganic hybrid nanometer film coating aluminum powder pigment and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100401627A CN101580653B (en) | 2009-06-10 | 2009-06-10 | Organic-inorganic hybrid nanometer film coating aluminum powder pigment and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101580653A true CN101580653A (en) | 2009-11-18 |
| CN101580653B CN101580653B (en) | 2012-05-09 |
Family
ID=41362975
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009100401627A Expired - Fee Related CN101580653B (en) | 2009-06-10 | 2009-06-10 | Organic-inorganic hybrid nanometer film coating aluminum powder pigment and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101580653B (en) |
Cited By (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101812249A (en) * | 2010-05-11 | 2010-08-25 | 长沙族兴金属颜料有限公司 | Resin-coated aluminum pigment and preparation method thereof |
| CN102127322A (en) * | 2010-12-24 | 2011-07-20 | 董前年 | Preparation method of double-layer coated water-based aluminum pigment |
| CN102516830A (en) * | 2011-11-25 | 2012-06-27 | 中山大学 | Method for preparing core-shell flaky aluminum powder-polyacrylic acid composite particles |
| CN103172966A (en) * | 2011-12-20 | 2013-06-26 | 抚顺易桂塑胶科技有限公司 | Preparation method of free-spraying silver flash ABS resin |
| CN103319916A (en) * | 2013-06-19 | 2013-09-25 | 中南大学 | Preparation method of inorganic-organic double-layer coated type aluminum paste |
| CN103360800A (en) * | 2013-08-07 | 2013-10-23 | 长沙族兴新材料股份有限公司 | High-floatage type water-based aluminium-silver paste and preparation method thereof |
| CN104277558A (en) * | 2014-09-29 | 2015-01-14 | 合肥旭阳铝颜料有限公司 | Anti-UV (anti-ultraviolet) aluminum pigment and preparation method thereof |
| CN104277566A (en) * | 2014-10-25 | 2015-01-14 | 合肥旭阳铝颜料有限公司 | Aluminum pigment with high sense of metal and preparation method thereof |
| CN104277560A (en) * | 2014-10-20 | 2015-01-14 | 合肥旭阳铝颜料有限公司 | Antirust water-based aluminum pigment and preparation method thereof |
| CN104292957A (en) * | 2014-10-27 | 2015-01-21 | 合肥旭阳铝颜料有限公司 | Waterproof magnetic aluminum pigment and preparation method thereof |
| CN104479425A (en) * | 2014-12-18 | 2015-04-01 | 常熟市环虹化工颜料厂 | Preparation method of water-based aluminum pigment |
| CN104817856A (en) * | 2015-05-18 | 2015-08-05 | 常德金鹏印务有限公司 | Water-based aluminum powder pigment, and preparation method and application thereof |
| CN104945983A (en) * | 2015-06-18 | 2015-09-30 | 成都纳硕科技有限公司 | UV-curable low-shrinkage environment-friendly coating |
| CN105482514A (en) * | 2015-12-15 | 2016-04-13 | 常熟市环虹化工颜料厂 | Method for preparing corrosion inhibition waterborne aluminum pigment |
| EP3050929A1 (en) * | 2015-01-28 | 2016-08-03 | Eckart GmbH | Coated pigments, method for their preparation and their use, coating agent and item |
| CN107099169A (en) * | 2017-05-16 | 2017-08-29 | 安徽大学 | A kind of preparation of cross-linking high molecular dye and the method that colored aluminum pigment is prepared with it |
| CN107964285A (en) * | 2017-12-22 | 2018-04-27 | 枞阳县三金颜料有限责任公司 | A kind of method for improving the resistance to temperature stability of water aluminum-silver slurry |
| CN109851457A (en) * | 2019-03-22 | 2019-06-07 | 湖北航天化学技术研究所 | A kind of automatically controlled solid propellant and preparation method thereof containing metal fuel |
| CN110204942A (en) * | 2019-06-03 | 2019-09-06 | 浙江大学 | Preparation method for marine environment metal surface normal temperature cure nano anticorrosive coating |
| CN111748224A (en) * | 2020-07-04 | 2020-10-09 | 上海灿达建材科技有限公司 | Aluminum powder coating for water-based paint and treatment process thereof |
| CN112480720A (en) * | 2020-11-26 | 2021-03-12 | 上海颜钛实业有限公司 | Preparation method of aluminum paste pigment and product prepared by preparation method |
| CN114681995A (en) * | 2020-12-25 | 2022-07-01 | 双乐颜料泰兴市有限公司 | Freeze-drying processing technology of pigment |
| CN116144215A (en) * | 2023-03-27 | 2023-05-23 | 湖南福瑞印刷有限公司 | High-gloss bright silver ink with transfer paper imitation effect and preparation method and application thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4750940A (en) * | 1985-09-07 | 1988-06-14 | Asahi Kasei Metals Limited | Novel resin-coated metallic pigment and a process for producing the same |
| CN1095488C (en) * | 2000-11-27 | 2002-12-04 | 山东迈英德化学有限公司 | Wet process for preparing aluminium powder pigment |
| CN100465235C (en) * | 2006-11-24 | 2009-03-04 | 华南理工大学 | Preparing method of coated aluminium powder pigment |
-
2009
- 2009-06-10 CN CN2009100401627A patent/CN101580653B/en not_active Expired - Fee Related
Cited By (33)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101812249A (en) * | 2010-05-11 | 2010-08-25 | 长沙族兴金属颜料有限公司 | Resin-coated aluminum pigment and preparation method thereof |
| CN102127322A (en) * | 2010-12-24 | 2011-07-20 | 董前年 | Preparation method of double-layer coated water-based aluminum pigment |
| CN102127322B (en) * | 2010-12-24 | 2013-01-02 | 董前年 | Preparation method of double-layer coated water-based aluminum pigment |
| CN102516830A (en) * | 2011-11-25 | 2012-06-27 | 中山大学 | Method for preparing core-shell flaky aluminum powder-polyacrylic acid composite particles |
| CN102516830B (en) * | 2011-11-25 | 2014-04-02 | 中山大学 | Method for preparing core-shell flaky aluminum powder-polyacrylic acid composite particles |
| CN103172966A (en) * | 2011-12-20 | 2013-06-26 | 抚顺易桂塑胶科技有限公司 | Preparation method of free-spraying silver flash ABS resin |
| CN103319916A (en) * | 2013-06-19 | 2013-09-25 | 中南大学 | Preparation method of inorganic-organic double-layer coated type aluminum paste |
| CN103319916B (en) * | 2013-06-19 | 2014-11-05 | 中南大学 | Preparation method of inorganic-organic double-layer coated type aluminum paste |
| CN103360800A (en) * | 2013-08-07 | 2013-10-23 | 长沙族兴新材料股份有限公司 | High-floatage type water-based aluminium-silver paste and preparation method thereof |
| CN104277558A (en) * | 2014-09-29 | 2015-01-14 | 合肥旭阳铝颜料有限公司 | Anti-UV (anti-ultraviolet) aluminum pigment and preparation method thereof |
| CN104277560B (en) * | 2014-10-20 | 2016-03-30 | 合肥旭阳铝颜料有限公司 | A kind of antirust based aluminum pigment and preparation method thereof |
| CN104277560A (en) * | 2014-10-20 | 2015-01-14 | 合肥旭阳铝颜料有限公司 | Antirust water-based aluminum pigment and preparation method thereof |
| CN104277566A (en) * | 2014-10-25 | 2015-01-14 | 合肥旭阳铝颜料有限公司 | Aluminum pigment with high sense of metal and preparation method thereof |
| CN104292957A (en) * | 2014-10-27 | 2015-01-21 | 合肥旭阳铝颜料有限公司 | Waterproof magnetic aluminum pigment and preparation method thereof |
| CN104479425A (en) * | 2014-12-18 | 2015-04-01 | 常熟市环虹化工颜料厂 | Preparation method of water-based aluminum pigment |
| CN107207877A (en) * | 2015-01-28 | 2017-09-26 | 埃卡特有限公司 | The pigment of coating, its production method and purposes, coating agent and article |
| EP3050929A1 (en) * | 2015-01-28 | 2016-08-03 | Eckart GmbH | Coated pigments, method for their preparation and their use, coating agent and item |
| WO2016120015A1 (en) * | 2015-01-28 | 2016-08-04 | Eckart Gmbh | Coated pigments, method for the production and the use thereof, coating agent and article |
| US10557037B2 (en) | 2015-01-28 | 2020-02-11 | Eckart Gmbh | Coated pigments, method for the production and the use thereof, coating agent and article |
| JP2018510228A (en) * | 2015-01-28 | 2018-04-12 | エッカルト ゲゼルシャフト ミット ベシュレンクテル ハフツングＥｃｋａｒｔ ＧｍｂＨ | Coated pigments, their manufacture and use, coating agents and articles |
| CN104817856A (en) * | 2015-05-18 | 2015-08-05 | 常德金鹏印务有限公司 | Water-based aluminum powder pigment, and preparation method and application thereof |
| CN104945983A (en) * | 2015-06-18 | 2015-09-30 | 成都纳硕科技有限公司 | UV-curable low-shrinkage environment-friendly coating |
| CN105482514A (en) * | 2015-12-15 | 2016-04-13 | 常熟市环虹化工颜料厂 | Method for preparing corrosion inhibition waterborne aluminum pigment |
| CN107099169B (en) * | 2017-05-16 | 2019-03-19 | 安徽大学 | A kind of preparation of cross-linking high molecular dye and the method for preparing colored aluminum pigment with it |
| CN107099169A (en) * | 2017-05-16 | 2017-08-29 | 安徽大学 | A kind of preparation of cross-linking high molecular dye and the method that colored aluminum pigment is prepared with it |
| CN107964285A (en) * | 2017-12-22 | 2018-04-27 | 枞阳县三金颜料有限责任公司 | A kind of method for improving the resistance to temperature stability of water aluminum-silver slurry |
| CN109851457A (en) * | 2019-03-22 | 2019-06-07 | 湖北航天化学技术研究所 | A kind of automatically controlled solid propellant and preparation method thereof containing metal fuel |
| CN110204942A (en) * | 2019-06-03 | 2019-09-06 | 浙江大学 | Preparation method for marine environment metal surface normal temperature cure nano anticorrosive coating |
| CN111748224A (en) * | 2020-07-04 | 2020-10-09 | 上海灿达建材科技有限公司 | Aluminum powder coating for water-based paint and treatment process thereof |
| CN112480720A (en) * | 2020-11-26 | 2021-03-12 | 上海颜钛实业有限公司 | Preparation method of aluminum paste pigment and product prepared by preparation method |
| CN114681995A (en) * | 2020-12-25 | 2022-07-01 | 双乐颜料泰兴市有限公司 | Freeze-drying processing technology of pigment |
| CN116144215A (en) * | 2023-03-27 | 2023-05-23 | 湖南福瑞印刷有限公司 | High-gloss bright silver ink with transfer paper imitation effect and preparation method and application thereof |
| CN116144215B (en) * | 2023-03-27 | 2024-03-15 | 湖南楠海科技有限公司 | High-gloss bright silver ink with transfer paper imitation effect and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101580653B (en) | 2012-05-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101580653B (en) | Organic-inorganic hybrid nanometer film coating aluminum powder pigment and preparation method and application thereof | |
| CN104558447B (en) | Inorganic nano composite anti-doodling resin and preparation method thereof | |
| CN100465235C (en) | Preparing method of coated aluminium powder pigment | |
| US8623503B2 (en) | Chromium-free rust-inhibitive surface treatment agent for metal parts with zinc surfaces and metal parts with zinc surfaces coated with rust-inhibitive surface coated film | |
| CN102863854B (en) | High chlorinated potyethlene anti-corrosive paint and preparation method thereof | |
| CN102146225B (en) | Waterborne room-temperature self-curing inorganic zinc enriched coating | |
| CN108034346A (en) | A kind of coating system for the composition and its formation for being used to produce aqueous coating | |
| CN109868026A (en) | A kind of Silicone-Modified Acrylate Resin and preparation method thereof and the hydrophobic weather-proof acrylic resin modified coating of sustained release | |
| CN106519920A (en) | Metal water-soluble anticorrosive coating | |
| TW201326327A (en) | Anti-reflection coating composition and process for preparing the same | |
| WO2018168947A1 (en) | Resin composition, molded article, laminate, gas barrier material, coating material, and adhesive | |
| CN106497286A (en) | A kind of metal anti-corrosive paint | |
| CN108997867A (en) | A kind of Environmental Protective Water-paint and preparation method thereof | |
| CN104293062B (en) | Soft raw matter antifouling paint of aqueous and preparation method thereof | |
| CN103122189A (en) | Heavy-duty anticorrosive coating for metal and method for preparing same | |
| CN110028862A (en) | A kind of compound super hydrophobic coating of modified Nano and preparation method thereof | |
| CN102898913A (en) | Aqueous inorganic zinc rich paint | |
| CN104893368A (en) | Coated modified aluminum powder pigment, and preparation method and use thereof | |
| CN106700662A (en) | Preparation method of acid/alkali-resistant corrosion-resistant aluminum pigment | |
| CN106497345A (en) | A kind of metal anticorrosive paint | |
| JP2002249705A (en) | Photocatalytic coating composition | |
| CN105331159A (en) | Coating for building external wall and preparation method thereof | |
| JP7368885B2 (en) | Water-based resin composition and coating film | |
| KR101069950B1 (en) | Steel Sheet Having Superior Electro-Conductivity and Resin Composition Therefor | |
| CN109913157A (en) | Environment-friendly type organosilicon-acrylate adhesive preparation method with light diffusion function and products thereof and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120509 Termination date: 20150610 |
|
| EXPY | Termination of patent right or utility model |