CN113522706B - Surface treatment color coating substrate suitable for radiation curing type color plate production process - Google Patents
Surface treatment color coating substrate suitable for radiation curing type color plate production process Download PDFInfo
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- CN113522706B CN113522706B CN202010299602.7A CN202010299602A CN113522706B CN 113522706 B CN113522706 B CN 113522706B CN 202010299602 A CN202010299602 A CN 202010299602A CN 113522706 B CN113522706 B CN 113522706B
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
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- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
- B05D5/06—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain multicolour or other optical effects
- B05D5/065—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain multicolour or other optical effects having colour interferences or colour shifts or opalescent looking, flip-flop, two tones
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- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
- C23C2/06—Zinc or cadmium or alloys based thereon
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/22—Electroplating: Baths therefor from solutions of zinc
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- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
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- C08J2461/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2461/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08J2461/32—Modified amine-aldehyde condensates
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- C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2471/02—Polyalkylene oxides
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K3/00—Use of inorganic substances as compounding ingredients
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Abstract
The invention discloses a surface treatment color coating substrate suitable for a radiation curing type color plate production process, which sequentially comprises the following components from a core part to the outside: the protective film comprises a substrate, a plating layer and a composite protective film, wherein the effective components of the composite protective film comprise: matrix resin: 55-70 parts by weight; a crosslinking agent: 1-6 parts by weight; compound electron beam irradiation resistant agent: 20-35 parts by weight; polyol containing at least 3 hydroxyl groups: 0.2-3 parts by weight; zirconium compound: 2-6 parts by weight; the water-soluble metal salt compound comprises the following components in parts by weight based on metal elements: 0.1-1 part. The surface of the color coating substrate is covered with a layer of composite protective film, the product has excellent surface wear resistance and rust resistance, and can be directly used for the production of a radiation curing type color coating process, and the surface protective film can effectively resist the damage of electron beam irradiation in the curing process of a color coating EB (Electron Beam) and realize the improvement of the adhesive force and the corrosion resistance between the substrate and a radiation curing coating.
Description
Technical Field
The invention relates to a metal material, in particular to a surface treatment color coating substrate.
Background
The production process of radiation curing type color coated steel plate is a color coating curing process which utilizes the energy irradiation of ultraviolet light (UV) or Electron Beam (EB) as the excitation source of the coating curing process in the color coated steel plate production process to make solvent-free paint instantly cured at normal temperature. Compared with the traditional thermosetting color coating production process, the radiation curing type color plate production process has the characteristics of environmental protection, energy conservation and high efficiency, and is a new direction for manufacturing color plates in the future.
Generally, in the production process of a radiation-curable color sheet, the thickness, color, and other characteristics of the topcoat layer determine the method of curing using Ultraviolet (UV) light, and complete curing of the topcoat layer cannot be achieved within a predetermined pass time, so that the method of curing the topcoat layer using Electron Beams (EB) is inevitable. While Electron Beam (EB) irradiation enables cross-linking cure of specially configured radiation-curable profile lacquer coatings, for most non-radiation-curable coatings, the large Electron Beam (EB) energy irradiation can cause damage to the chemical bonds in the coating, resulting in degradation and failure of the coating.
Therefore, if the conventional color coating pretreatment method is still adopted to carry out surface treatment on the substrate before radiation curing, in the subsequent finish paint EB curing process, the high-energy electron beams can damage the pretreatment layer, so that the adhesion and corrosion resistance between the substrate and the color coating layer are lost, and the product quality is seriously influenced. If the coating and curing of the coating are directly carried out without carrying out surface treatment on the substrate, good adhesion and corrosion resistance between the surfaces of various substrates and the radiation curing coating cannot be ensured.
Therefore, in order to successfully commercialize the radiation-curable color plate, it is desirable to obtain a surface-treated color-coated substrate suitable for the production process of the radiation-curable color plate, so as to improve the adhesion and corrosion resistance between the substrate and the coating layer.
Disclosure of Invention
The invention aims to provide a surface treatment color-coated substrate suitable for a radiation curing type color plate production process, which has excellent surface wear resistance and rust resistance, and can be directly used for the production of the radiation curing type color-coated process.
In order to achieve the above object, the present invention provides a surface-treated color-coated substrate suitable for a radiation-curable color sheet production process, comprising, in order from a core portion to the outside: the protective film comprises a substrate, a plating layer and a composite protective film, wherein the effective components of the composite protective film comprise:
matrix resin: 55-70 parts by weight;
a crosslinking agent: 1-6 parts by weight;
compound electron beam irradiation resistant agent: 20-35 parts by weight;
polyol containing at least 3 hydroxyl groups: 0.2-3 parts by weight;
a zirconium compound: 2-6 parts by weight;
the water-soluble metal salt compound comprises the following components in parts by weight based on metal elements: 0.1-1 part.
Further, in the surface treatment color-coated substrate of the present invention, the effective components thereof are composed of the following:
matrix resin: 55-70 parts by weight;
a crosslinking agent: 1-6 parts by weight;
compound electron beam irradiation resistant agent: 20-35 parts by weight;
polyol containing at least 3 hydroxyl groups: 0.2-3 parts by weight;
a zirconium compound: 2-6 parts by weight;
the water-soluble metal salt compound comprises the following components in parts by weight based on metal elements: 0.1-1 part.
In the above-described aspect, the inventors have creatively devised a surface-treated color-coated substrate suitable for a radiation-curing type color sheet production process, the color-coated substrate comprising, in order from a core portion to the outside: a substrate, a plating layer and a composite protective film. The composite protective film can ensure that the color-coated substrate has excellent inter-process surface damage resistance and antirust performance, can resist the damage of electron beam radiation energy in the subsequent radiation curing process of a primer or a finish coat, and effectively improves the adhesive force and the corrosion resistance between the substrate and the radiation curing coat. The color-coated substrate has excellent surface wear resistance and antirust performance, and can be directly used for the production of a radiation curing color-coating process.
The matrix resin adopted in the technical scheme of the invention is a high molecular weight anionic polyurethane resin based on aromatic isocyanate, and the matrix resin can form a basic framework of the composite protective film. The matrix resin adopts polyurethane resin based on aromatic isocyanate, and has higher benzene ring density compared with polyurethane resin based on aliphatic isocyanate, so that the formed protective film has better mechanical resistance, and the wear resistance of the protective film in the links of product packaging, transportation, storage, uncoiling and the like is improved. Meanwhile, the flexibility of the polyurethane resin prevents the protective film from being too fragile. In addition, hydroxyl and carboxyl in the matrix resin have high reactivity and can react with a cross-linking agent, so that the cross-linking density of the protective film is improved, and the corrosion resistance is improved. In the technical scheme, the reason why the weight part of the matrix resin is controlled to be 55-70 parts is as follows: when the weight part is less than 55 parts, the abrasion resistance of the composite protective film is reduced; when the weight part is more than 70 parts, the compactness of the composite protective film is influenced, and the corrosion resistance of the composite protective film is reduced.
In the above aspect, the crosslinking agent used in the present invention is a compound that can react with the carboxyl group and the hydroxyl group in the matrix resin. The cross-linking agent can mainly perform cross-linking reaction with matrix resin, and aims to further increase the cross-linking density of the protective film in the curing process and improve the compactness of the protective film, so that the cured protective film has better corrosion resistance. In the technical scheme of the invention, the weight part of the cross-linking agent is controlled to be 1-6 parts because: when the weight part is less than 1 part, the crosslinking effect with the matrix resin is not obvious, and the curing degree of the generated protective film is not enough, so that the abrasion resistance and the corrosion resistance of the protective film are reduced; when the weight part is more than 6 parts, the crosslinking reaction between the crosslinking agent and the matrix resin is too strong, the brittleness of the protective film is too high, and the protective film is easily peeled off after deformation, resulting in poor adhesion to the coating after deformation.
The whole composite protective film of the color-coated substrate disclosed by the invention has electron beam irradiation resistance, can still keep excellent adhesion performance and corrosion resistance with the substrate and the primer after electron beam irradiation in the subsequent primer or finish curing process, and has inseparable action with a compound electron beam irradiation resisting agent in the composite protective film. In the technical scheme of the invention, the weight part of the compound electron beam resistant irradiation agent is controlled to be 20-35 parts because: when the weight part is less than 20 parts, the repair of the crosslinking degree of the protective film after electron beam irradiation is insufficient, and the adhesion and corrosion resistance between the substrate and the primer coating are reduced; when the amount is more than 35 parts by weight, the proportion of the matrix resin is lowered, and the abrasion resistance of the protective film is not ensured.
In the technical scheme of the invention, the adopted polyhydric alcohol containing at least 3 hydroxyl groups can further promote the crosslinking density of the surface-milled protective film and improve the comprehensive resistance of the protective film. In the technical scheme of the invention, the weight part of the polyhydric alcohol containing at least 3 hydroxyl groups is controlled to be 0.2-3 parts because: when the weight part is less than 0.2 parts, the effect of improving the resistance of the protective film is insignificant, and when the weight part is more than 3 parts, the ductility of the protective film may be deteriorated.
In the above scheme, the zirconium compound in the technical scheme of the invention can play a role in corrosion inhibition in the protective film, and can further perform cross-linking polymerization with carboxyl in the matrix resin, so as to increase the adhesion performance of the protective film. In the technical scheme of the invention, the weight part of the zirconium compound is controlled to be 2-6 parts because: when the weight part is less than 2 parts, the corrosion resistance and adhesion of the protective film may be deteriorated, and when the weight part is more than 6 parts, the brittleness of the protective film is too large, and the protective film may be easily peeled off after deformation, resulting in deterioration of adhesion to the coating layer after deformation.
In the technical scheme of the invention, the adopted water-soluble metal salt compound mainly has the function of providing the under-film corrosion inhibition function. In the technical scheme, the weight parts of the water-soluble metal salt compound are controlled to be 0.1-1 part because: when the weight part is less than 0.1 part, the corrosion resistance of the protective film may be reduced, and when the weight part is more than 1 part, the adhesion of the protective film may be deteriorated.
Furthermore, in the surface treatment color-coated substrate, the compound electron beam irradiation resistant agent is prepared by compounding modified epoxy acrylate prepolymer and acrylate monomer.
Further, in the surface treatment color-coated substrate, the compound type electron beam irradiation resisting agent is obtained by mixing the modified water-based epoxy acrylate prepolymer and the water-soluble acrylate monomer at the temperature of 30-50 ℃ for 5-15min and then compounding.
In the technical scheme of the invention, the compound electron beam resistant irradiation agent is prepared by compounding the modified epoxy acrylate prepolymer and the acrylate monomer, because after the protective film is irradiated by electron beams, part of the structure of the cured and crosslinked matrix resin in the protective film is damaged by high-energy electrons, which is mainly reflected in the damage to structures such as C-C, C-O and the like in a matrix resin chain segment, so that the overall crosslinking degree of the protective film is reduced and radiation degradation is formed. The modified epoxy acrylate prepolymer and the acrylate monomer in the compound electron beam resisting irradiation agent are irradiated by electron beams and cannot be damaged, and high-energy electrons can enable unsaturated double bonds in an acrylic acid structure to generate free radicals and initiate free radical polymerization. Thereby further improving the crosslinking density of the whole protective film and repairing the insufficiency of the integrity of the protective film caused by the damage of the matrix resin by the irradiation of electron beams. The protective film repaired by free radical polymerization is matched with higher crosslinking density, so that the adhesive force and corrosion resistance of the surface of the substrate and the primer coating are ensured.
Further, in the surface treatment color-coated substrate of the invention, the weight ratio of the epoxy acrylate prepolymer to the acrylate monomer is 4.0-8.0.
In the surface treatment color-coated substrate, the weight ratio of the epoxy acrylate prepolymer to the acrylate monomer is controlled to be 4.0-8.0, and if the weight ratio of the epoxy acrylate prepolymer to the acrylate monomer is lower than 4.0, after electron beam irradiation, the protection film is too brittle and is easy to fall off after deformation, so that the adhesion between the protection film and a coating layer after deformation is poor; if the weight ratio of the epoxy acrylate prepolymer to the acrylate monomer exceeds 8.0, the repair of the crosslinking degree of the protective film after electron beam irradiation may be insufficient, and the under-film spreading corrosion performance after the coating is combined may be insufficient.
Further, in the surface-treated color-coated substrate of the present invention, the modified epoxy acrylate prepolymer is selected from the group consisting of: any one of dibasic acid modified epoxy acrylate prepolymer, maleic anhydride modified epoxy acrylate prepolymer, ether modified epoxy acrylate prepolymer, ester modified epoxy acrylate prepolymer, dihydroxy modified epoxy acrylate prepolymer and polyol modified epoxy acrylate prepolymer.
Further, in the surface treatment color-coated substrate of the present invention, the acrylate monomer is selected from: 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, N-methylolacrylamide, trimethylolpropane triacrylate, polyethylene glycol (200) dimethacrylate, polyethylene glycol (400) dimethacrylate, and polyethylene glycol (600) dimethacrylate.
Further, in the surface-treated color-coated substrate according to the present invention, the matrix resin includes an aromatic isocyanate-based anionic aqueous polyurethane resin having a molecular weight of 5000 to 8000.
Furthermore, in the surface treatment color-coated substrate, the acid value of the anionic waterborne polyurethane resin is 15-30KOH/g, and the hydroxyl value is 70-110KOH/g.
Further, in the surface-treated color-coated substrate of the present invention, the crosslinking agent is selected from at least one of the following: urea-formaldehyde resin etherified with methanol, epoxy modified amino resin, carbodiimide, polyaziridine and water-based isocyanate.
Further, in the surface treatment color-coated substrate of the present invention, the boiling point of the polyol having at least 3 hydroxyl groups is 230 to 310 ℃.
Further, in the surface-treated color-coated substrate of the present invention, the zirconium compound includes at least one of potassium zirconium carbonate and zinc ammonium zirconium carbonate.
Further, in the surface-treated color-coated substrate of the present invention, the water-soluble metal salt compound includes at least one of a vanadium salt compound and a titanium salt compound.
The water-soluble metal salt compound includes at least one of a vanadium salt compound and a titanium salt compound. Wherein the valence of vanadium in the vanadium compound can be any one of the +2 to +5 valence range, the source of vanadium compound can be oxide, such as vanadium (V) oxide, vanadium (III) oxide, etc., or fluoride salt, such as vanadium (IV) fluoride, vanadium (V) fluoride, or ammonium metavanadate, etc.; the titanium element in the titanium compound can be provided by a fluorine-containing titanium compound.
Furthermore, in the surface treatment color-coated substrate, the weight of the composite protective film is 0.5-1.8g/m per single surface 2 。
Further, in the surface treatment color-coated substrate of the present invention, the plating layer is: hot galvanizing, hot aluminum zinc plating, electrogalvanizing or hot galvanizing aluminum magnesium.
Compared with the prior art, the surface treatment color-coated substrate suitable for the radiation curing type color plate production process has the following advantages and beneficial effects:
the invention provides a surface treatment color-coated substrate suitable for a radiation curing type color plate production process, wherein the surface of the substrate is covered with an environment-friendly organic-inorganic composite protective film, the color-coated substrate has excellent surface wear resistance and antirust performance and can be directly used for the production of the radiation curing type color coating process, and in the process of curing a color coating EB (Electron Beam), the surface protective film can effectively resist the damage of electron beam irradiation and realize the improvement of the adhesive force and the corrosion resistance between the substrate and a radiation curing coating.
Detailed Description
A surface-treated color-coated substrate suitable for a radiation-curable color plate production process according to the present invention will be further explained and illustrated with reference to specific examples, which, however, should not be construed as unduly limiting the technical aspects of the present invention.
Examples 1 to 8 and comparative examples 1 to 8
In the present invention, the color coated substrates of examples 1 to 8 and comparative examples 1 to 6 comprise, in order from the core portion to the outside: cold rolling a substrate, front and back plating layers, and front and back environment-friendly organic-inorganic composite protective films. Specific information on the kinds of plating layers, the components and parts by weight of the protective films, and the weights of the protective films of the color coated substrates of examples 1 to 8 and comparative examples 1 to 6 is shown in table 1.
Further, comparative example 7 in the present invention is a color coated substrate which was not subjected to any surface treatment, i.e., comparative example 7 was a hot-dip aluminum-zinc plated layer without a protective film.
In addition, comparative example 8 is a color coated substrate of a hot-dip aluminum-zinc plated layer treated by a conventional pretreatment process in a thermosetting type color coating production. The conventional pretreatment process comprises the steps of spraying a composite film-forming agent with Co and Ni as film-forming elements on the surface of a coating substrate, and then spraying and sealing by using a chromate passivating agent to obtain a pretreatment layer, wherein the content of the Co and Cr elements in the pretreatment layer is Co:3-7mg/m 2 ；Cr：15-25mg/m 2 。
Table 1 shows the specific information of the kind of plating, the composition and the parts by weight of the protective film, and the weight of the protective film of examples 1 to 8 and comparative examples 1 to 6.
Table 1.
* Note: the matrix resin is anionic water polyurethane resin based on aromatic isocyanate with molecular weight of 5000-8000, and has acid value of 15-30KOH/g and hydroxyl value of 70-110KOH/g; the cross-linking agent is one of urea-formaldehyde resin etherified with methanol, epoxy modified amino resin, carbodiimide, polyethylenimine and water-based isocyanate, and optimally, carbodiimide is adopted; the compound electron beam radiation resistant agent is obtained by compounding C1 and C2 after mixing for 10min at the temperature of 45 ℃, wherein the C1 is any one of dibasic acid modified waterborne epoxy acrylate prepolymer, maleic anhydride modified waterborne epoxy acrylate prepolymer, ether modified waterborne epoxy acrylate prepolymer, ester modified waterborne epoxy acrylate prepolymer, dihydroxy modified waterborne epoxy acrylate prepolymer and polyol modified waterborne epoxy acrylate prepolymer, such as maleic anhydride modified waterborne epoxy acrylate prepolymer, and the C2 is any one of 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, N-hydroxymethyl acrylamide, trimethylolpropane triacrylate, polyethylene glycol (200) dimethacrylate, polyethylene glycol (400) dimethacrylate and polyethylene glycol (600) dimethacrylate, such as N-hydroxymethyl acrylamide; the polyhydric alcohol containing at least 3 hydroxyl groups can be any one of 2-hydroxymethane-2-methyl-1,3 propylene glycol, pentaerythritol, glycerol or trimethylolpropane; the zirconium compound is one of potassium zirconium carbonate or ammonium zinc zirconium carbonate, preferably potassium zirconium carbonate; the water-soluble metal salt compound is at least one of a vanadium salt compound and a titanium salt compound, such as one or more of ammonium metavanadate, sodium metavanadate, vanadyl oxalate and ammonium fluotitanate.
The color-coated substrates obtained in examples 1 to 8 and comparative examples 1 to 8 were sampled, cut into standard size samples, and tested as follows, so as to obtain test data for evaluating each property thereof, wherein the specific test items and test methods are as follows:
1) Abrasion resistance:
1. the surface is repeatedly rubbed by a steel ball method and stainless steel with the diameter of 10mm, the load is 100g, the rubbing speed is 150mm/min, the rubbing distance is 10mm, and the reciprocating rubbing is carried out for 50 times, and the evaluation criteria are as follows:
very good: after 50 times of reciprocating friction, the surface friction coefficient is less than or equal to 0.15
O: after 50 times of reciprocating friction, the surface friction coefficient is more than 0.15 and less than or equal to 0.3
Δ: after 50 times of reciprocating friction, the surface friction coefficient is more than 0.3 and less than or equal to 0.4
X: after 50 times of reciprocating friction, the surface friction coefficient is more than 0.4
2. The surface was repeatedly rubbed with a rubber plane having a diameter of 10mm by a rubber method at a load of 500g, a rubbing speed of 300m/min, a rubbing distance of 20mm, and 50 times of reciprocal rubbing, and the evaluation criteria were as follows:
very good: no change of surface protective film
O: small scratch of protective film
Δ: multiple scratches on the protective film
X: the protective film completely falls off
2) Corrosion resistance:
1. salt spray resistance: the plate neutral salt spray test was carried out according to ASTM B117 for 120h, and the evaluation criteria were as follows:
very good: the area ratio of white rust is less than or equal to 5 percent
O: the white rust area rate is more than 5 percent and less than or equal to 10 percent
Δ: the white rust area ratio is more than 10 percent and less than or equal to 50 percent
X: the area ratio of white rust is more than 50 percent
2. Moisture and heat resistance: two samples are stacked and placed by adopting a lamination damp-heat method, a moment of 30 N.m is applied, the samples are placed in a damp-heat box with the temperature of 49 ℃ and the humidity of 98% for 240h, and the evaluation criteria are as follows:
very good: the area ratio of white rust is less than or equal to 1 percent
O: the white rust area ratio is more than 1 percent and less than or equal to 5 percent
Δ: the white rust area rate is more than 5 percent and less than or equal to 30 percent
X: the area ratio of white rust is more than 30 percent
3) Electron beam irradiation resistance:
irradiating a color coated substrateAnd coating and curing the primer and the finish of the curing type color coating. Wherein the primer adopts Ultraviolet (UV) curing type paint, the film thickness is 5 mu m, and the curing condition UV dose =500mJ/m 2 (ii) a The finish paint is Electron Beam (EB) cured paint, the film thickness is 15 mu m, the EB dose under the curing condition reaches 100KGy at most, and the voltage reaches 200KV at most. And (3) carrying out the following adhesion performance tests of T bending, hundred lattices, impact, poaching and the like on the sample plate after full coating, and carrying out the corrosion resistance tests of flat plate salt spray, under-film diffusion corrosion and the like. The test result of the adhesion and the corrosion resistance can directly reflect the electron beam irradiation resistance of the surface protective film of the color coated substrate.
1.T bend: according to the 7-bending test standard in GB/T13448, the evaluation standard is as follows:
◎：≤3T
○：4T
Δ：5T
×：≥6T
2. hundred grids: the method is carried out according to 13-grid test standard in GB/T13448, and the evaluation standard is as follows:
very good: the rating of the marking test is GB/T13448 with the 0 rating specified in Table 1
O: the rating of the grid test is GB/T13448, grades 1-2 specified in Table 1
Δ: the rating of the marking test is 3-4 grades specified in GB/T13448 Table 1
X: the rating of the marking test is 5 grades specified in GB/T13448 Table 1
3. Impact: according to the 8-reverse impact test standard in GB/T13448, the evaluation standard is as follows:
very good: so that the maximum impact energy of the coating without cracking or falling is more than or equal to 9J
O: the maximum impact energy for preventing the coating from cracking and falling is 7 to 8J
Δ: so that the maximum impact energy of the coating without cracking and falling is 6 to 7J
X: so that the maximum impact energy of the coating without cracking and falling is less than or equal to 6J
4. Boiling in water: immersing the sample plate in boiling water for 2h, taking out, evaluating the foaming or falling condition of the appearance of the coating, and carrying out a check test according to 13 in GB/T13448, a check test standard:
very good: the coating has no bubbling and no shedding, and the rating of the marking test is 0 grade specified in GB/T13448 Table 1
O: the coating has little bubbling and no shedding, and the rating of the marking test is 1-2 grades specified in GB/T13448 Table 1
Δ: the coating is largely foamed and has no shedding, and the rating of the marking test is 3 to 4 grades specified in GB/T13448 Table 1
X: the coating was largely peeled off and rated by the crosshatch test as grade 5 as specified in Table 1 of GB/T13448
5. Plane salt spray: according to ASTM B117, time 1000h, evaluation criteria:
very good: the bubble density and bubble size should not be greater than 2 of GB/T1766, as defined in Table 21
O: the bubble density and size should not be greater than 3 of GB/T1766, table 21
Δ: the bubble density grade and bubble size should not be greater than 4 of GB/T1766 as defined in Table 21
X: the bubble density grade and the bubble size are not more than 5 grades specified in table 21 of GB/T1766
6. Under-film etching performance: before the test, a single straight line parallel to the long side of the sample is scribed by a small knife at the middle part of the sample, the length is not less than 50mm, the scribing is to be performed through the coating, the distance between the scribing and the side part is not less than 30mm, then the salt spray test is performed according to ASTM B117, the time is 1000h, and the evaluation standard is as follows:
very good: the unilateral average expanding erosion width of the lineation part is less than or equal to 5mm
O: the average expanding erosion width of one side of the lineation part is more than 5mm and less than or equal to 10mm
Δ: the average expanding erosion width of one side of the lineation part is more than 10mm and less than or equal to 15mm
X: the unilateral average expanding erosion width of the lineation part is more than 15mm
Table 2 lists the relevant performance parameters for the color coated substrate samples of examples 1-8 and comparative examples 1-8 after the above tests.
TABLE 2
As can be seen from table 2, after the various tests on the samples of the color-coated substrates in examples 1 to 8 of the present invention, the evaluation results are "x" and "o", and all surfaces have good inter-process surface damage resistance and good anti-rust performance, and the protective film thereon can resist the damage of electron beam radiation energy in the subsequent curing process of the EB topcoat, so as to effectively improve the adhesion and the corrosion resistance between the substrate and the coating.
Furthermore, combining table 2 and table 1, it can be seen that in comparative example 1, the addition of the matrix resin in an excessive amount, which is more than the amount of the matrix resin with which the crosslinking agent can be cured, affects the densification of the protective film, resulting in a decrease in the corrosion resistance of the protective film, as compared with examples 1 to 8. And due to the insufficient addition of the compound electron beam irradiation resistant agent, the electron beam irradiation resistance of the protective film is reduced, and the crosslinking degree of the protective film is not repaired enough after electron beam irradiation in the curing process of EB (Electron Beam) finish paint, so that the adhesive force and corrosion resistance between a coated substrate and a coating are reduced. In addition, in comparative example 2, the wear resistance of the protective film was lowered due to insufficient addition of the matrix resin. In comparative example 3, the addition amount of the crosslinking agent was significantly insufficient, the crosslinking effect was not significant, and the degree of curing of the protective film was insufficient, resulting in a decrease in the abrasion resistance and corrosion resistance of the protective film. In comparative example 4, the ratio of C1 to C2 was too low, as noted with reference to table 1, i.e., the weight ratio of epoxy acrylate prepolymer to the acrylate monomer was too low, the protective film was too brittle after electron beam irradiation, and the protective film was easily peeled off after deformation, which resulted in poor adhesion between the substrate and the coating after deformation of the coated sample. In comparative example 5, the ratio of C1 to C2 was too high, and it is noted with reference to table 1 that the weight ratio of the epoxy acrylate prepolymer to the acrylate monomer was too high, resulting in insufficient repair of the degree of crosslinking of the protective film after electron beam irradiation and insufficient under-film spreading properties after bonding with the coating. In comparative example 6, no metal salt compound was added, resulting in a decrease in the corrosion resistance of the protective film. In comparative example 7, since the substrate was not subjected to any surface treatment, the corrosion resistance of the substrate was significantly insufficient, and the adhesion and corrosion resistance between the substrate and the coating layer after the radiation curable coating material was coated were not ensured. In comparative example 8, after the substrate subjected to the conventional color coating pretreatment was irradiated with electron beams in the subsequent curing process of the EB topcoat, high-energy electrons seriously damaged the conventional pretreatment chemical conversion layer on the substrate, resulting in loss of adhesion and corrosion resistance between the coated substrate and the coating.
It should be noted that the above-mentioned embodiments are only specific embodiments of the present invention. It is apparent that the present invention is not limited to the above embodiments and similar changes or modifications can be easily made by those skilled in the art from the disclosure of the present invention and shall fall within the scope of the present invention.
Claims (10)
1. A surface-treated color-coated substrate suitable for a radiation-curable color sheet production process, comprising, in order from a core portion to the outside: the protective film comprises a substrate, a plating layer and a composite protective film, wherein the composite protective film comprises the following effective components:
matrix resin: 55-70 parts by weight;
a crosslinking agent: 1-6 parts by weight;
compound electron beam irradiation resistant agent: 20-35 parts by weight;
polyol containing at least 3 hydroxyl groups: 0.2-3 parts by weight;
zirconium compound: 2-6 parts by weight; the zirconium compound comprises at least one of potassium zirconium carbonate and zinc ammonium zirconium carbonate;
the water-soluble metal salt compound comprises the following components in parts by weight based on metal elements: 0.1-1 part;
the compound electron beam irradiation resistant agent is obtained by mixing modified waterborne epoxy acrylate prepolymer and water-soluble acrylate monomer at the temperature of 30-50 ℃ for 5-15min and compounding; the weight ratio of the epoxy acrylate prepolymer to the acrylate monomer is 4.0-8.0;
the matrix resin comprises anionic waterborne polyurethane resin based on aromatic isocyanate with molecular weight of 5000-8000.
2. The surface-treated color-coated substrate according to claim 1, wherein the active ingredient thereof is composed of:
matrix resin: 55-70 parts by weight;
a crosslinking agent: 1-6 parts by weight;
compound electron beam irradiation resistant agent: 20-35 parts by weight;
polyol containing at least 3 hydroxyl groups: 0.2-3 parts by weight;
zirconium compound: 2-6 parts by weight; the zirconium compound comprises at least one of potassium zirconium carbonate and zinc ammonium zirconium carbonate;
the water-soluble metal salt compound comprises the following components in parts by weight based on metal elements: 0.1-1 part.
3. The surface treated color coated substrate of claim 1, wherein the modified epoxy acrylate prepolymer is selected from the group consisting of: any one of a dibasic acid modified epoxy acrylate prepolymer, a maleic anhydride modified epoxy acrylate prepolymer, an ether modified epoxy acrylate prepolymer, an ester modified epoxy acrylate prepolymer, a dihydroxy modified epoxy acrylate prepolymer and a polyol modified epoxy acrylate prepolymer.
4. The surface treated color coated substrate of claim 1, wherein the acrylate monomer is selected from the group consisting of: 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, N-methylolacrylamide, trimethylolpropane triacrylate, polyethylene glycol (200) dimethacrylate, polyethylene glycol (400) dimethacrylate, and polyethylene glycol (600) dimethacrylate.
5. The surface-treated color-coated substrate according to claim 4, wherein the anionic aqueous polyurethane resin has an acid value of 15 to 30KOH/g and a hydroxyl value of 70 to 110KOH/g.
6. The surface treated color coated substrate of claim 1 or 2, wherein the crosslinking agent is selected from at least one of: urea-formaldehyde resin etherified with methanol, epoxy modified amino resin, carbodiimide, polyaziridine and water-based isocyanate.
7. The surface-treated color-coated substrate according to claim 1 or 2, wherein the polyol having at least 3 hydroxyl groups has a boiling point of 230 to 310 ℃.
8. The surface-treated color-coated substrate according to claim 1 or 2, wherein the water-soluble metal salt compound comprises at least one of a vanadium salt compound and a titanium salt compound.
9. The surface-treated color-coated substrate according to claim 1 or 2, wherein the composite protective film has a weight of 0.5 to 1.8g/m per single surface 2 。
10. The surface-treated color-coated substrate according to claim 1 or 2, wherein the plating layer is: hot galvanizing, hot aluminum zinc plating, electrogalvanizing or hot galvanizing aluminum magnesium.
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