CN1110524C - Aqueous paint with flash metal luster - Google Patents
Aqueous paint with flash metal luster Download PDFInfo
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- CN1110524C CN1110524C CN98111238A CN98111238A CN1110524C CN 1110524 C CN1110524 C CN 1110524C CN 98111238 A CN98111238 A CN 98111238A CN 98111238 A CN98111238 A CN 98111238A CN 1110524 C CN1110524 C CN 1110524C
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- aqueous paint
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Abstract
The present invention relates to aqueous paint with flash metal luster. The aqueous paint is prepared from (1) an aqueous medium, (2) an internal crosslinking microparticle polymer dispersed in (1) the aqueous medium, (3) an aqueous crosslinking agent and (4) a metal pigment or a quasi-metal pigment or an inorganic pigment or an organic pigment dispersed in the aqueous medium, wherein the aqueous medium contains organic solvent and has volatility, and the particle diameter of the internal crosslinking microparticle polymer is from 0.05 to 0.5 mum. The luster of a coating layer is improved, and the coating layer has higher flashing effect by the spraying technology of two times of coating and one time of baking; the aqueous paint can be widely used for coating systems with multiple layers of paint of automobiles and component parts of the automobiles, and the aqueous paint has less influence on environmental pollution.
Description
The present invention relates to aqueous paint with flash metal luster, be specially adapted to the surface layer application of automobile.
At present, be coated with in the baking metallized coating system two, base coat still is that coating varnish all adopts solvent-borne type, and base coat requires thick film (wet film) application, is beneficial to the required high retraction volume of tinsel orientations, adds the sedimentation that cellaburate prevents sagging and metal charge usually, but, add cellaburate and cause amount of solid very low, organic solvent content is very high, influences environmental issue.The aqueous paint with flash metal luster of United States Patent (USP) 4403003 and the 4493914 crosslinked micropartical aqueous polymer dispersions that adopt, its crosslinked micropartical is to exist down by a kind of stearic acid stablizer, in aqueous medium, make by dispersion polymerization ethylene type unsaturated monomer, but its complex process, reach man-hour more than 40 hours, the industrialization difficulty, European patent EP 287144 discloses the atomic moisture type of a kind of two-step approach letex polymerization polymkeric substance, has nucleocapsid structure, but can not form the internal crosslinking structure, thereby the spraying coating varnish is after on the bottom, and it is unresolved that varnish easily sinks to the problem that bottom reduces coating film gloss.
The purpose of this invention is to provide a kind of aqueous paint with flash metal luster that contains the core-shell emulsion of internal crosslinking polymeric microsphere, can present required pseudo-plasticity and high gloss when being used for automobile metal sparkling paint.
Realize that the object of the invention technical scheme is: a kind of aqueous paint with flash metal luster, its component are by a kind of volatile aqueous medium 84.10% that contains organic solvent; A kind of water insoluble, but be scattered in internal crosslinking micropartical polymkeric substance in the above-mentioned aqueous medium, particle diameter is 0.05～0.5 μ ml1.64%; A kind of water cross-linking agent 1.75%; Be scattered in metallic pigment or metallike pigment or mineral dye or pigment dyestuff 2.51% composition in the above-mentioned aqueous medium, above percentage ratio all is weight percentage.
The present invention introduces in the aqueous paint with flash metal luster with the core-shell emulsion that contains the internal crosslinking polymeric microsphere, because the high crosslinked of particle can improve the physical and mechanical properties of filming, required pseudo-plasticity of anti-sag or thixotropy also are provided, these special particle interactions have reduced the sedimentation of coating composition significantly, be coated with a baking base coat/coating varnish system for two simultaneously, avoided varnish to sink to the phenomenon that base coat reduces gloss, because its flash effect of metallized coating is subjected to the influence of metallic pigment orientations, the degree that is parallel to ground is high more, flash effect is good more, general wet film volume can shrink to the greatest extent to greatest extent, viscosity should increase as far as possible rapidly after coating cloud reached base material, to reduce, influence flash effect owing to the caused confusion that rearranges of turbulent flow.For this reason, the aqueous paint with flash metal luster solids content also should be enough low, well is orientated when shrinking with assurance, should have pseudo-plasticity or thixotropy simultaneously, though can obtain thixotropy by adding the thixotropic agent method, but can not solve coating varnish and sink to the bottom problem,, make aqueous paint with flash metal luster have structural viscosity by adopting cross-linked polymer particle, obtain pseudo-plasticity, bottom is filmed stop the Hui Rong of coating varnish, improved the gloss of coating, and have higher flash effect.
For a kind of its main ingredient of internal crosslinking micropartical polymkeric substance that is insoluble to but is scattered in the aqueous medium be: (A) contain a kind of multifunctional vinyl monomer at least with two unsaturated groups, as dialkylene benzene, ethylene glycol bisthioglycolate (methyl) acrylate, hexylene glycol two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, tetramethylol methane tetraacrylate; (B) contain a kind of simple function monomer at least, as (methyl) acrylic acid hydroxy alkyl ester, n-methylolacrylamide, vinyl cyanide, vinylformic acid, methacrylic acid, glycidyl methacrylate; (C) contain two kinds of non-functional monomers at least, as (methyl) acrylic acid C1-18 base ester; (D) initiator and emulsifying agent.The weight percent of its main ingredient is (A) multifunctional ethene monomer 0.5～5%, is lower than 0.5%, and then the particle degree of crosslinking of Xing Chenging is low excessively, be difficult for producing structural viscosity, too high greater than the 5% particle degree of crosslinking that forms, react wayward, be easy to generate grumeleuse, (B) simple function ethene monomer 3～20% is lower than 3%, and then cross-linking density is low after the film forming, the poor durability of filming, be higher than 20%, then cross-linking density is too high, the coating machine degradation.(C) non-functional monomer 60～95%, (D) initiator and emulsifying agent 0.5～10%, wherein (A) and 95% (C) forms nuclear, (B) and surplus (C) composition shell.
Can adopt aminoresin for its component of aqueous paint with flash metal luster (3) water cross-linking agent, as product or this reaction product C with trimeric cyanamide, urea, benzene croak amine and formaldehyde, Paraformaldehyde 96 building-up reactions
1-4Alcohols part or the aminoresin that forms of full etherificate.
Can form with the organic solvent that water dissolves each other by water and some for a kind of volatile aqueous medium that contains organic solvent of its component of aqueous paint with flash metal luster (1), its organic solvent is the C1-4 alcohols, ethylene glycol, the monoether of propylene glycol or bis ether kind solvent, best is low toxicity or nontoxic solvent such as propyl carbinol, sec-butyl alcohol, propylene glycol first (second, fourth) ether.
Be scattered in metallic pigment in the pigment of aqueous medium such as aluminium powder, copper powder, zinc powder for its component of aqueous paint with flash metal luster (4); Metallike pigment such as various pearly pigment; Mineral dye such as superfine titanic oxide, carbon black, transparent ferric oxide series pigments; Pigment dyestuff is a quinacridone, phthalocyanine system, azo system.
Aqueous paint with flash metal luster of the present invention, the polymerization technique of its component (2) cross-linked polymer particle be have tensio-active agent in the presence of, cause decomposition by water soluble starter and carry out radical polymerization, tensio-active agent is cationic surfactant such as alkyl sulfonic ester salt, aniorfic surfactant such as Sodium dodecylbenzene sulfonate, nonionic surface active agent such as shrink Sorbitol Powder stearate, zwitterionics such as MS-1 (negatively charged ion and non-ionic type).Above-mentioned polymerization technique adopts the step-by-step polymerization method, forms " seed " emulsion earlier and forms stratum nucleare, drips other ethene monomer then and forms shell, thereby obtain to have the emulsion of nucleocapsid structure.The second-order transition temperature Tg of stratum nucleare structure is 20～50 ℃, the second-order transition temperature Tg-10 of shell structure～30 ℃, become the stage to introduce multifunctional ethene monomer at karyomorphism, make nuclear have crosslinking structure, temperature of reaction is 50～100 ℃, and the hydroxyl value that emulsion forms is 30～100, acid number 10～50, emulsion solids content is 15～50%, and particle diameter is controlled at 0.05～0.5 μ m.
The present invention is applied to substrate surface and sprays, base material can be materials such as iron and steel or aluminium alloy, also can scribble negative electrode or anodic electro-priming in advance or further spray inter coat at substrate surface, on inter coat, spray aqueous paint with flash metal luster of the present invention then, through the short period of time low-flash, general flash vaporization point is 30～100 ℃, the best is 60～90 ℃, time is 5～15 minutes, temperature wind circulation, the scope of warm wind control be wind speed (rice/minute) * time (branch) * temperature (℃) be 500～1000.Construction road number is 2 roads, and 50～60% of first road spraying total film thickness sprays coating varnish again after twice have sprayed.
The invention will be further described below by embodiment.But the present invention is not limited to this.Quantity among the embodiment is weight part.
The preparation of preparation example 1 crosslinked micropartical aqueous polymer dispersion
Agitator, thermometer, reflux exchanger and logical N are being housed
2Add 101.20 parts of deionized waters in the four-hole boiling flask of gas device, 0.50 part of MS-1 (10%) aqueous solution, when being heated to 80 ℃, add 1.06 parts of butyl acrylates, 1.01 parts of methyl methacrylates, be warmed up to 80～85 ℃, reacted 15 minutes, and added 6.06 part of 10% ammonium persulfate aqueous solution then, be incubated and form " seed " emulsion that is strong blue phase after 30 minutes, and then drip pre-emulsion (I), dripped off in 3 hours, and be incubated 1 hour, drip pre-emulsion (II), dripped off in 1 hour, be incubated half an hour, drip (III) again, dripped off in 15 minutes, be incubated 2 hours, cool to room temperature filters with 200 order nylon cloths, obtains the sub-emulsion of stable cross-linked polymer particle, non-volatile content is 22.01%, and median size is 0.15 μ m.
The component of pre-emulsion (I):
Butyl acrylate 11.81
Methyl methacrylate 20.70
Glycol diacrylate 1.01
MS-1 0.29
Deionized water 22.10
Ammonium persulphate 0.03
The component of pre-emulsion (II):
Methacrylic acid 0.5
Butyl acrylate 1.91
Hydroxyethyl methylacrylate 2.12
MS-1 0.20
Deionized water 11.71
(III) component:
Shrink Sorbitol Powder monostearate 0.03
Ammonium persulphate 0.03
Deionized water 6.20
In above-mentioned preparation example 1, can use glycol diacrylate instead Viscoat 295.
Embodiment 1
Step (a): the pH value of crosslinked micropartical aqueous polymer dispersion is regulated:
28.85 parts of dispersion liquids that add preparation example 1 in the container that band stirs, 10.00 parts of deionized waters drip the mixture of 0.20 part of dimethylethanolamine and 3.46 parts of deionized waters again, stir and obtain pH value 7.67 after 15 minutes, non-volatile content 15.9% dispersion liquid.
Step (b): the preparation of aluminium pigment slurry
In the container that band stirs, add (65%) 2.42 part of aluminium paste, propylene glycol monomethyl ether stirs for 3.50 parts and adds 2.50 parts of propylene glycol monomethyl ethers after 30 minutes, stirs 30 minutes, adds Cymel3701.10 part then, 2.00 parts of polypropylene glycols (molecular weight 400) continue to stir filtration discharging in 1 hour.
Step (c): aqueous paint with flash metal luster preparation
With 425.10 parts of the crosslinked micropartical polymer aqueous dispersions of above-mentioned steps (a), 100.21 parts of the aluminium pigment of step (b), deionized water mixes for 20.37 parts, stirs 45 minutes, regulate pH value to 7.67, solids content 17.0% with 10%-dimethyl ethanol amine aqueous solution then.Be aqueous paint with flash metal luster of the present invention.
The application of embodiment 2 aqueous paint with flash metal luster
To paint in the metal foil precoating, spray aqueous paint with flash metal luster then, 25 ℃ of the temperature that controls environment, ambient moisture 65%, spraying thickness 16 μ m (dry film), 80 ℃ of flash distillations 5 minutes, 1.5 meters/minute of wind speed, and then spray 2 times have sprayed and have been cooled to room temperature, spray coating varnish again, room temperature flash distillation 2 minutes was solidified 30 minutes down at 140 ℃, its appearance of film planeness is good, specular gloss is 90 for 20 °, and the flash metal luster effect is good, does not have obvious sagging phenomenon.The environmental pollution influence is very little, and the dress that can be widely used in automobile and part accessory thereof especially is coated with.
Claims (5)
1, a kind of aqueous paint with flash metal luster is characterized in that, it by:
(1) a kind of volatile aqueous medium 84.10% that contains organic solvent;
(2) a kind of water insoluble, but be scattered in internal crosslinking micropartical polymkeric substance in the aqueous medium of above-mentioned (1), particle diameter is 0.05～0.5 μ ml1.64%;
(3) a kind of water cross-linking agent 1.75%;
(4) be scattered in metallic pigment in above-mentioned (1) aqueous medium or metallike pigment or mineral dye or pigment dyestuff 2.51% is formed, above percentage ratio all is weight percentage.
2, aqueous paint with flash metal luster according to claim 1 is characterized in that, the component of the internal crosslinking micropartical polymkeric substance in the component (2) and the weight percent of each component are as follows:
(A) contain a kind of multifunctional ethene monomer 0.5～5% at least with two unsaturated groups;
(B) contain a kind of monofunctional ethene monomer 3～20% at least;
(C) contain two kinds of non-functional monomers 60～95% at least;
(D) initiator and emulsifying agent 0.5～10%;
Wherein (A) and 95% (C) forms nuclear, (B) and surplus (C) composition shell.
3, aqueous paint with flash metal luster according to claim 2 is characterized in that, internal crosslinking micropartical polymkeric substance, and its preparation technology adopts the step-by-step polymerization method, forms " seed " emulsion earlier and forms stratum nucleare, drips the ethene monomer then and forms shell.
4, aqueous paint with flash metal luster according to claim 2, it is characterized in that, the second-order transition temperature of its stratum nucleare of internal crosslinking micropartical polymkeric substance is 20～50 ℃, and the second-order transition temperature of shell is-10～30 ℃, and the second-order transition temperature of stratum nucleare will exceed 10 ℃ of shell second-order transition temperatures at least.
5, aqueous paint with flash metal luster according to claim 1, it is characterized in that, it has been applied to finishing paint layered coating system, adopt two to be coated with baking method curing, flash conditions is 60～90 ℃ of temperature before the Lacquer finish, time is 5～10 minutes, the circulation of warm wind, the scope of warm wind control be wind speed (rice/minute) * temperature (℃) * time (branch) is 500～5000.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98111238A CN1110524C (en) | 1998-04-09 | 1998-04-09 | Aqueous paint with flash metal luster |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98111238A CN1110524C (en) | 1998-04-09 | 1998-04-09 | Aqueous paint with flash metal luster |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1231311A CN1231311A (en) | 1999-10-13 |
| CN1110524C true CN1110524C (en) | 2003-06-04 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98111238A Expired - Fee Related CN1110524C (en) | 1998-04-09 | 1998-04-09 | Aqueous paint with flash metal luster |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101190964B (en) * | 2006-11-24 | 2010-08-18 | 上海涂料有限公司技术中心 | Process for preparing high-hydroxyl-value polyester resin |
| JP5276829B2 (en) * | 2006-12-19 | 2013-08-28 | 新日鐵住金ステンレス株式会社 | Conductive clear coated stainless steel sheet |
| CN101077954B (en) * | 2007-06-26 | 2010-05-19 | 广东雅图化工有限公司 | Automobile metal sparkling paint and preparation method thereof |
| CN102464847A (en) * | 2010-11-15 | 2012-05-23 | 上海锦湖日丽塑料有限公司 | Resin composition and preparation method thereof |
| CN103059673A (en) * | 2012-12-27 | 2013-04-24 | 王娟 | Sparkling metallic paint |
| CN103319965B (en) * | 2013-07-02 | 2015-12-23 | 中国海洋石油总公司 | A kind of automobile water-based property metal flash paint and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0256391A2 (en) * | 1986-08-20 | 1988-02-24 | The Glidden Company | Thermosetting emulsion polymers |
| JPH036269A (en) * | 1989-06-02 | 1991-01-11 | Honny Chem Ind Co Ltd | Aqueous emulsion of core-shell resin for manufacturing matte electrodeposition coating composition and preparation of the same emulsion |
| JP3006269B2 (en) * | 1992-03-17 | 2000-02-07 | 松下電器産業株式会社 | Zinc alkaline battery |
-
1998
- 1998-04-09 CN CN98111238A patent/CN1110524C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0256391A2 (en) * | 1986-08-20 | 1988-02-24 | The Glidden Company | Thermosetting emulsion polymers |
| JPH036269A (en) * | 1989-06-02 | 1991-01-11 | Honny Chem Ind Co Ltd | Aqueous emulsion of core-shell resin for manufacturing matte electrodeposition coating composition and preparation of the same emulsion |
| JP3006269B2 (en) * | 1992-03-17 | 2000-02-07 | 松下電器産業株式会社 | Zinc alkaline battery |
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| Publication number | Publication date |
|---|---|
| CN1231311A (en) | 1999-10-13 |
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Owner name: CNOOC CHANGZHOU PAINT + COATINGS INDUSTRY RESEARCH Free format text: FORMER NAME: CHANGZHOU INST. OF PAINT CHEMICAL INDUSTRY, MINISTRY OF CHEMICAL INDUSTRY |
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Address after: 213016 Changzhou Zhong Road, Jiangsu Province, No. 22 Longjiang Road Patentee after: CNOOC Changzhou Paint & Coatings Industry Research Institute Address before: 213016 Airport Road, Jiangsu, Changzhou Patentee before: Changzhou Inst. of Paint Chemical Industry, Ministry of Chemical Industry |
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Granted publication date: 20030604 Termination date: 20140409 |