CN109321011B - UV-curable metal coil coating first-layer primer and preparation method thereof - Google Patents
UV-curable metal coil coating first-layer primer and preparation method thereof Download PDFInfo
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- CN109321011B CN109321011B CN201811131443.9A CN201811131443A CN109321011B CN 109321011 B CN109321011 B CN 109321011B CN 201811131443 A CN201811131443 A CN 201811131443A CN 109321011 B CN109321011 B CN 109321011B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
- B05D7/26—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials synthetic lacquers or varnishes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/002—Priming paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
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- Application Of Or Painting With Fluid Materials (AREA)
Abstract
The invention provides a UV-curable metal coil coating first-layer primer and a preparation method thereof, which solve the problem that a UV coating is difficult to adhere to metal. The components are as follows: diluting monomer, initiator and metal adhesion promoter. The coating is coated on a metal coil by roll coating, and is cured by ultraviolet irradiation to obtain the primary primer of the coil coating. The adhesive force and the impact resistance of the UV coating for the metal coiled material are solved.
Description
Technical Field
The invention relates to the field of UV (ultraviolet) photocureable coatings of coiled materials, in particular to a first primer of a UV coating of a metal coiled material and a preparation method thereof.
Background
The traditional coil paint is polyurethane baking paint, and epoxy amino type, epoxy polyurethane type, polyester amino type and polyester polyurethane type are often heated to 200-400 ℃ during construction, so that great environmental pollution and energy waste are caused. The ultraviolet curing coating and the technology have the characteristics of 4E: excellent performance, energy saving, environmental protection and economy. In response to the call for social protection from the environment, it is necessary to apply UV curable coatings to the coil. However, adhesion of the coating to the substrate is a prerequisite for the use of the coating. Coil coating requirements include: the coating is resistant to scratching, boiling and forward and reverse impact, particularly, the scratching resistance reaches the level 0, the boiling resistance requires that the coating does not crack or fall off after boiling for two hours, and the forward and reverse impact resistance requires that the coating does not crack or fall off after impact. Unlike the adhesion of stoving varnish polyurethane to metal, the adhesion of UV coatings to metal and its promotion are unknown, and some common metal adhesion promoters such as oligomers of phosphate react with metal through phosphate groups. In experiments, the phosphate adhesion promoter can only be added by 1-3 wt%, and the addition of the phosphate adhesion promoter is not beneficial to the requirements of water boiling and the like. In addition, we have also found that the phosphate ester acts on the metal leaving "stains" and these areas of action are weak points of adhesion. Therefore, the design of the metal UV light-cured coating only by the metal adhesion promoter is far from enough, and a new visual angle is needed for developing the metal UV coating.
Marine mussels are aquatic organisms that strongly adhere to the surface of any substance (organic and inorganic) underwater by secreting an adhesive protein, and scientists have found that poly-dopamine-like substances are responsible for adhesion in marine mussels (science,318,426). This characteristic of polydopamine has caused a hot tide of surface modification of various materials by technologists worldwide. However, studies on the use of dopamine for UV coatings for coils have not been reported.
Disclosure of Invention
The invention aims to provide a UV-curable metal coil coating first-layer primer and a preparation method thereof, wherein the UV-curable metal coil coating first-layer primer can be UV-cured on a metal coil and has extremely strong adhesive force, can be used for the adhesion of a subsequent metal UV coating, and solves the problem of the construction of the adhesive force of the UV coating on metal.
The technical scheme of the invention is as follows: the first primer of the UV-curable metal coil coating comprises the following raw materials in parts by mass:
diluting monomers: 30-65 parts;
photoinitiator 1173: 3-6 parts;
metal adhesion promoter: 30-80 parts;
wherein the diluent monomer is a water-soluble oligomer EO15-TMPTA (15 ethoxylated trimethylolpropane triacrylate); the metal promoter is dopamine buffer solution.
The dopamine buffer solution is a dopamine aqueous solution added with sodium periodate, and the pH value is adjusted to 8-12 by using dilute alkali.
The concentration of the dopamine in the dopamine buffer solution is 40-500mg.L-1The concentration of the sodium periodate is 80-1000mg.L-1。
The dilute alkali is NaOH aqueous solution.
The method for preparing the first primer of the UV-curable metal coil coating is characterized in that all components are uniformly mixed and adjusted to the required viscosity.
The method for using the first primer of the UV-curable metal coil coating is characterized in that the coating is coated on a coil in a rolling way, and UV irradiation is carried out for 1-5 minutes to form an adhesive film with strong adhesive force on metal.
The first primer of the UV-curable metal coil coating is applied to metal coils of iron, aluminum or alloys thereof.
Has the advantages that:
the UV-cured primer for the first layer of the coiled material prepared by the invention is fast in curing, good in adhesive force on the metal coiled material, good in compatibility and interface contact force on the UV coating of the subsequent coiled material, and effectively improves the adhesive force of the UV-cured coating on the metal coiled material.
In the method, the pH value of the solution is controlled to be kept alkaline after the dopamine is regulated by sodium periodate and sodium hydroxide so as to ensure that the dopamine forms a compact adhesive film on the coiled material through UV irradiation in the presence of a water-soluble diluent and a photoinitiator. The adhesive film has obvious compatibility and extremely high adhesive force to the UV coating. The dopamine polymer film produced here, as a transition layer between the coil and the UV coating, is different from the effect of adding dopamine in other coatings, such as in the patent CN107828328A modified aqueous polyurethane coating, the dopamine plays a role of surface polymerization modified graphene.
Drawings
FIG. 1: the Fourier infrared spectrum of the dopamine powder before and after UV irradiation on a metal plate has the abscissa of wave number and the ordinate of transmittance.
FIG. 2: the light yellow left image is the UV curable coil primer solution (before irradiation) and the black right image is after irradiation. FIG. 3: and after the first layer of dopamine primer is made on the coiled material, loading the UV coating and the colored paint in sequence, and measuring the adhesive force by a grid drawing method to obtain a photo.
FIG. 4: after the first layer of dopamine primer is made on the coiled material, the coiled material is loaded with UV coating and colored paint in sequence, and photos are obtained after positive and negative impact.
FIG. 5: and after the first layer of dopamine primer is made on the coiled material, sequentially loading a UV coating and a colored paint, and taking a photograph after water boiling resistance.
FIG. 6: and (3) taking phosphate as an adhesion promoter, sequentially loading the UV coating and the colored paint, and taking a picture after boiling for 2 hours.
Detailed Description
A first primer of a UV-curable coil coating and a preparation method thereof are disclosed, which comprises the following components:
diluting monomer
Photoinitiator
Metal adhesion promoter
Wherein the oligomer is a water-soluble diluent monomer EO 15-TMPTA;
said photoinitiator is 1173;
the metal promoter is a treated dopamine solution.
The metal promoter is dopamine aqueous solution and sodium periodate aqueous solution, NaOH solution is used as pH regulator, and the pH is adjusted to 8-12.
The metal promoter is dopamine aqueous solution with concentration of 10-500mg.L-1The concentration of the sodium periodate is 20-1000mg.L-1The concentration of the pH regulator NaOH solution is 1-4mol-1。
The first primer of the UV-curable coil coating comprises the following steps: the components are mixed evenly and adjusted to the required viscosity. The second step is that: the coating is rolled on a coiled material, and UV irradiation is carried out for 1-5 minutes, so that an adhesive film with strong adhesive force is formed on the metal.
The coating is suitable for metal coils, and the metal belongs to metal coils of iron, aluminum and alloys thereof.
Example 1
The formulation of the coil top primer for UV curing is given in table one:
TABLE-UV-CURABLE COAL PRIMING PAINT FORMULATIONS
The pH of the solution 1 was adjusted to 8.5 with 4M NaOH solution. The three solutions 1,2 and 3 are mixed according to the proportion in the table and fully stirred. The mixture is coated on a coiled material in a rolling way, UV irradiation is carried out for 2 minutes, the coiled material coated by the dopamine polymer is obtained, and the infrared spectrum of the obtained dopamine polymer is researched.
And (3) infrared spectrum characterization: wave number range 600-4000cm-1. The Fourier-Infrared Transmission Peak (FTIR) of the resulting film on the web is shown in FIG. 1. It can be seen that the dopamine in powder form has many infrared transmission peaks (a), and most of the infrared transmission peaks disappear (b) after the polymerization is completed. Only 1643cm remain-1The peak at (a), corresponding to the vibrational mode of C ═ O, is an isomer of the vicinal diphenol (OH-) on dopamine, consistent with the fact that dopamine polymerization does not alter the vicinal diphenol.
Example 2
The formulation of the coil top primer for UV curing is given in table two:
TABLE II UV-CURABLE COAL PRIMING PAINT FORMULATIONS FOR COILED MATERIALS
The pH of the solution 1 was adjusted to 9 with 4M NaOH solution. Mixing the three solutions 1,2 and 3 according to the proportion of the second table, and fully stirring. And rolling and coating the mixture primer on a coiled material, and carrying out UV irradiation for 1 minute to obtain the dopamine polymer coated coiled material.
The mixture primer was subjected to UV irradiation, and the results are shown in fig. 2. The left panel is before UV irradiation and the right panel is after UV irradiation, dopamine is itself a small molecule, which absorbs light more after polymerization into a large molecule, and thus the color deepens. This phenomenon is also displayed on the web.
Example 3
The formulation of the coil top primer for UV curing is as follows:
formula of first layer primer of coiled material capable of being UV cured
The pH of the solution 1 was adjusted to 9 with 4M NaOH solution. Mixing the three solutions 1,2 and 3 according to the proportion of table three, and fully stirring. And rolling and coating the mixture on a coiled material, and carrying out UV irradiation for 1.5 minutes to obtain the dopamine polymer coated coiled material. After UV coating and colored paint loading and curing are carried out subsequently, the adhesive force is tested by a grid cutting method, the result is shown in figure 3, and the adhesive force is tested by a GB/T13448-.
Example 4
The formulation of the coil top primer for UV curing is given in table four:
TABLE IV UV-CURABLE COAL PRIMING PAINT FORMULATIONS
The pH of the solution 1 was adjusted to 10 with 4M NaOH solution. Mixing the three solutions 1,2 and 3 according to the proportion of the four components in the table, and fully stirring. And rolling and coating the mixture on a coiled material, and carrying out UV irradiation for 1.5 minutes to obtain the dopamine polymer coated coiled material. After the subsequent UV coating and color paint loading and curing, the result of the impact-resistant coil coating is obtained, as shown in FIG. 4, the reverse impact resistance is achieved according to GB/T13448-2006, the punch diameter is 3mm, and the impact energy is 5 NM.
Example 5
The formulation of the coil top primer for UV curing is shown in table five:
TABLE V UV-CURABLE COAL PRIMING PAINT FORMULATIONS
The pH of the solution 1 was adjusted to 10 with 4M NaOH solution. Mixing the three solutions 1,2 and 3 according to the proportion shown in the table five, and fully stirring. And rolling and coating the mixture on a coiled material, and carrying out UV irradiation for 3 minutes to obtain the coiled material coated with the dopamine polymer. After the subsequent UV coating and color paint loading and curing, the coil coating result of water boiling resistance is obtained, as shown in FIG. 5, the phenomenon of peeling or falling does not occur when boiling water is boiled for two hours according to GB/T13448-2006. For comparison, using phosphate as an adhesion promoter, skin breaks occurred after poaching, as shown by the dashed circle in fig. 6.
Claims (6)
1. The first primer of the UV-curable metal coil coating is characterized by comprising the following raw materials in parts by mass:
diluting monomers: 30-65 parts;
photoinitiator 1173: 3-6 parts;
metal adhesion promoter: 30-80 parts;
wherein the diluent monomer is a water-soluble oligomer EO 15-TMPTA; the metal promoter is a dopamine buffer solution, the dopamine buffer solution is a dopamine aqueous solution added with sodium periodate, and the pH value is adjusted to 8-12 by using dilute alkali.
2. The primer coat for a UV curable metallic coil coating of claim 1, wherein the dopamine in said buffered dopamine solution is in the range of 40 to 500mg.L-1The concentration of the sodium periodate is 80-1000mg.L-1。
3. The primer coat for a UV curable metallic coil coating of claim 1, wherein said dilute base is NaOH in water.
4. The method for preparing the primer for the first layer of the UV-curable metal coil coating according to any one of claims 1 to 3, wherein the components are mixed and adjusted to a desired viscosity.
5. A method of using the primer coat of UV curable metallic coil coating of any of claims 1 to 3, wherein the coating is roll coated onto a coil and UV irradiated for 1 to 5 minutes to form a strong adhesive film on the metal.
6. Use of the primer coat of the UV curable metallic coil coating of any one of claims 1 to 3 for metallic coils of iron, aluminum or alloys thereof.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811131443.9A CN109321011B (en) | 2018-09-27 | 2018-09-27 | UV-curable metal coil coating first-layer primer and preparation method thereof |
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| CN109321011B true CN109321011B (en) | 2021-02-02 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101844993A (en) * | 2010-05-21 | 2010-09-29 | 北京化工大学 | Photo-curing monomer with ortho-phenolic hydroxyl structure, preparation method and bond thereof |
| CN104369505A (en) * | 2014-10-27 | 2015-02-25 | 北京兴通力得科技有限公司 | Light-curing heavy corrosion protection roll material and preparation method thereof |
| CN107522827A (en) * | 2017-09-20 | 2017-12-29 | 杨军 | A kind of photocuring 3D printing photosensitive resin and its preparation method and application |
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| US20030087985A1 (en) * | 1990-10-15 | 2003-05-08 | Hubbell Jeffrey A. | Gels for encapsulation of biological materials |
| KR101285301B1 (en) * | 2011-10-17 | 2013-07-11 | 한국교통대학교산학협력단 | Antibacterial coating compound and composition comprising the same |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101844993A (en) * | 2010-05-21 | 2010-09-29 | 北京化工大学 | Photo-curing monomer with ortho-phenolic hydroxyl structure, preparation method and bond thereof |
| CN104369505A (en) * | 2014-10-27 | 2015-02-25 | 北京兴通力得科技有限公司 | Light-curing heavy corrosion protection roll material and preparation method thereof |
| CN107522827A (en) * | 2017-09-20 | 2017-12-29 | 杨军 | A kind of photocuring 3D printing photosensitive resin and its preparation method and application |
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Address after: 313000 Liangshan Road 159, Linghu Town Industrial Function Zone, Nanxun District, Huzhou City, Zhejiang Province Applicant after: Ruitong polymer technology (Zhejiang) Co., Ltd Address before: 313018 No. 159, Ling Shan Road, industrial zone, Linghu Town, Nanxun District, Huzhou, Zhejiang Applicant before: Zhejiang Ruitong photoelectric material Co Ltd |
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