CN112662284A - Radiation curing coating for household appliance metal plate and application thereof - Google Patents
Radiation curing coating for household appliance metal plate and application thereof Download PDFInfo
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Classifications
-
- 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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
- C09D163/10—Epoxy resins modified by unsaturated compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
- Laminated Bodies (AREA)
Abstract
The invention relates to a radiation curing coating for a household appliance metal plate and application thereof, which comprises a UV radiation curing bottom coating for forming a semi-hardened surface bottom layer and an electron beam radiation curing surface coating for forming a surface hardened layer; the UV radiation curing primer mainly comprises polyurethane modified epoxy acrylic resin, vinyl acetate, multi-arm cardanol-based epoxy resin, cross-linking resin and a photoinitiator; the electron beam radiation curing surface layer coating mainly comprises polyurethane modified epoxy acrylic resin, carbon-containing decaborane cyanate resin, acrylic acid modified polyester, multi-arm cardanol-based epoxy resin and cross-linked resin; the content of the electron beam radiation curing surface layer coating in the coating is below 30 percent. The coating disclosed by the invention is high in curing efficiency, low in energy consumption, environment-friendly, good in adhesive force, flexibility, weather resistance, impact resistance, external force scratch resistance, repeated bending resistance and flexibility, free of cracking after being bent to a certain degree, smooth in hand feeling and especially suitable for the surface of a metal substrate.
Description
Technical Field
The invention belongs to the technical field of radiation curing coatings, and particularly relates to a radiation curing coating for a metal plate of a household appliance, and a preparation method and application thereof.
Background
At present, with the gradual improvement of environmental protection consciousness of people, the photocureable coating is widely applied as a new generation of environment-friendly coating. The Ultraviolet (UV) light curing coating is used for curing resin through UV light irradiation, and the system does not contain Volatile Organic Compounds (VOC), so that the curing speed is high, and the efficiency is high. But the UV energy consumption is large, a radiation blind area exists on a workpiece with a complex shape, effective curing cannot be realized, the curing thickness of the UV coating is limited to 20-40 mu m, deep curing is not thorough, the adhesion between the coating and a base material is not strong, and the corrosion resistance and the mechanical property are reduced.
Electron beam curing (EB) is a process in which a high-energy electron beam generated by an electron accelerator is used as a radiation source to induce liquid oligomers to undergo cross-linking polymerization to rapidly form a solid product. EB curing is a room temperature curing technology, the curing thickness of the EB curing is 100-1000 mu m, the energy consumption is low, VOC is not contained, and the environmental pollution is avoided. Compared with other curing modes, the EB technology has the advantages of high curing speed, strong penetrating power, low energy consumption, excellent coating performance and the like, and is widely applied to the fields of coatings, adhesives, printing ink and the like. EB products can be treated immediately after radiation curing, so that the production efficiency is greatly improved, and the physical properties of the cured products are improved. Thus, EB curing has become a new environmentally friendly curing technology developed after UV curing.
For example, chinese patent CN101117458 discloses an ultraviolet light or electron beam initiated curing coating, and chinese patent CN101845243 discloses a low energy electron beam radiation curing coating. In both patent documents, electron beam radiation curing techniques are disclosed, and the related technical solutions can overcome some of the disadvantages of UV curing techniques to some extent; however, electron beam cured coatings still suffer from various drawbacks, such as the use of photoinitiators, resulting in a more odorous coating; the adhesion between the coating and the base material is relatively poor, the applicable surface of the base material is relatively narrow, and the like.
Disclosure of Invention
The invention aims to provide an electron beam radiation curing coating for a metal plate of a household appliance on the basis of the prior art, which can solve the problems that a UV curing coating is not completely cured in a deep layer, the curing efficiency is low, the adhesion force between a coating and a metal base material is not strong, the coating is easy to fall off, the weather resistance and the impact resistance are poor, the service life is short, the corrosion resistance and the mechanical property are poor, and the coating is difficult to apply to the surface of the metal plate of the household appliance, so that the coating has good adhesion force, flexibility, weather resistance, impact resistance, external force scratch resistance, repeated bending resistance and flexibility, can be bent to a certain degree without cracking, has smooth hand feeling, and is particularly suitable for the surface of the metal plate of the household appliance.
It is still another object of the present invention to provide the use of the above radiation curable coating for coating the surface of a metal plate for household appliances.
The technical scheme of the invention is as follows:
a radiation-curable coating for household electrical appliance metal plates comprises a UV radiation-curable primer for forming a semi-cured surface primer and an electron beam radiation-curable topcoat for forming a surface-cured layer; wherein,
the UV radiation curing primer takes polyurethane modified epoxy acrylic resin, vinyl acetate, multi-arm cardanol-based epoxy resin, cross-linked resin and a photoinitiator as main materials;
the electron beam radiation curing surface layer coating mainly comprises polyurethane modified epoxy acrylic resin, carbon-containing decaborane cyanate resin, acrylic acid modified polyester, multi-arm cardanol-based epoxy resin and cross-linked resin;
the content of the electron beam radiation curing surface layer coating in the coating is below 30 percent.
Preferably, the electron beam radiation curing surface coating further comprises polyaspartic acid ester.
The method combines two technologies of UV radiation curing and electron beam radiation curing, takes UV coating as a substrate, firstly forms a semi-hardened surface, then coats an electron beam curing coating on the semi-hardened surface, and simultaneously cures the semi-hardened substrate and the surface layer in an electron beam curing mode, thereby forming a coating film with high strength and excellent performance.
In the coating of the present application, the photoinitiator in the UV radiation curable primer cannot be used in excess or at conventional levels, preferably at levels below 0.5%, so that a semi-cured substrate surface can be obtained upon curing. In order to obtain a better semi-hardened surface, the curing time of the UV radiation curing primer is generally less than 0.4s, so that the curing rate of the coating is less than 80%, and the primer in a semi-cured state is formed. When the electron beam curing coating is coated on the semi-cured bottom coating and electron beam radiation curing is carried out, the semi-cured bottom coating and the surface layer can be cured simultaneously, the using amount of the photoinitiator can be greatly reduced under the condition that most of the UV coating accounts for the UV coating, the curing time is shortened, and the curing efficiency is improved.
Preferably, the thickness of the coating layer when the UV radiation-curable primer is applied is 150 μm or less, the thickness of the coating layer when the electron beam radiation-curable top coat is applied is 65 μm or less, and the thickness of the electron beam radiation-curable top coat may be 5 to 65 μm, preferably 5 to 35 μm.
The curing reaction of the UV coating in this application is different from conventional UV light curing reactions, which require that a semi-hardened surface is achieved which is not fully cured, and which, if a hardened surface is obtained, may damage the base coating in a subsequent curing reaction. The curing energy of the UV radiation curing primer needs to be 100mJ/cm during curing2The curing time is below 0.3 s; the conditions for curing the electron beam radiation curing surface coating are as follows: the radiation voltage is 380-420 KeV; the electron beam dose is 35-45 KGy; the beam current is 90-120 mA; the radiation curing temperature is 20-30 ℃, and a bottom coating and a surface coating in a complete curing state can be formed under the condition.
In a preferred scheme, the UV radiation curing primer coating comprises the following components in parts by weight: 45-60 parts of polyurethane modified epoxy acrylic resin; 30-40 parts of vinyl acetate; 10-20 parts of multi-arm cardanol-based epoxy resin; 10-20 parts of a cross-linked resin; 25-35 parts of an active diluent; 5-9 parts of an adhesion promoter; 0.2-0.7 part of photoinitiator; and the content of the photoinitiator is less than 0.5 percent.
In a more preferred embodiment, the UV radiation-curable primer coating comprises the following components in parts by weight: 45-56 parts of polyurethane modified epoxy acrylic resin; 32-40 parts of vinyl acetate; 12-20 parts of multi-arm cardanol epoxy resin; 10-15 parts of a cross-linked resin; 27-31 parts of a reactive diluent; 5.2-8.1 parts of an adhesion promoter; 0.2-0.6 part of photoinitiator; and the content of the photoinitiator is less than 0.5 percent.
In a preferred scheme, the electron beam radiation curing surface coating comprises the following components in parts by weight: 25-40 parts of polyurethane modified epoxy acrylic resin; 15-25 parts of carbon-containing decaborane cyanate resin; 10-20 parts of acrylic acid modified polyester; 15-25 parts of multi-arm cardanol-based epoxy resin; 8-15 parts of a cross-linked resin; 25-35 parts of an active diluent; 4.6-8.6 parts of an adhesion promoter; 1.4-2.8 parts of a filler; 2.2-3.4 parts of high molecular weight polyurethane dispersant; 0.6-1.6 parts of an auxiliary agent.
In a preferred scheme, the electron beam radiation curing surface coating comprises the following components in parts by weight: 25-40 parts of polyurethane modified epoxy acrylic resin; 15-25 parts of carbon-containing decaborane cyanate resin; 5-10 parts of acrylic acid modified polyester; 15-25 parts of multi-arm cardanol-based epoxy resin; 8-15 parts of a cross-linked resin; 4-9 parts of polyaspartic acid ester; 25-35 parts of an active diluent; 4.6-8.6 parts of an adhesion promoter; 1.4-2.8 parts of a filler; 2.2-3.4 parts of high molecular weight polyurethane dispersant; 0.6-1.6 parts of an auxiliary agent.
In a more preferable scheme, the electron beam radiation curing surface coating comprises the following components in parts by weight: 30-40 parts of polyurethane modified epoxy acrylic resin; 20-25 parts of carbon-containing decaborane cyanate resin; 10-20 parts of acrylic acid modified polyester; 20-25 parts of multi-arm cardanol-based epoxy resin; 8-15 parts of a cross-linked resin; 30-35 parts of an active diluent; 4.6-8.6 parts of an adhesion promoter; 1.4-2.8 parts of a filler; 2.2-3.4 parts of high molecular weight polyurethane dispersant; 0.6-1.6 parts of an auxiliary agent.
In another preferred scheme, the electron beam radiation curing surface coating comprises the following components in parts by weight: 30-40 parts of polyurethane modified epoxy acrylic resin; 20-25 parts of carbon-containing decaborane cyanate resin; 5-10 parts of acrylic acid modified polyester; 20-25 parts of multi-arm cardanol-based epoxy resin; 8-15 parts of a cross-linked resin; 4-9 parts of polyaspartic acid ester; 30-35 parts of an active diluent; 4.6-8.6 parts of an adhesion promoter; 1.4-2.8 parts of a filler; 2.2-3.4 parts of high molecular weight polyurethane dispersant; 0.6-1.6 parts of an auxiliary agent.
The preparation method of the UV radiation curing primer coating and the electron beam radiation curing surface coating is that all the components are uniformly stirred at the temperature of 30-40 ℃.
The radiation curing coating of the invention comprehensively adopts two curing forms of UV radiation curing and electron beam radiation curing, but not the simple superposition of the two curing forms, the method firstly adopts a small amount of photoinitiator in the UV radiation curing primer, then adopts a very short curing time to realize the incomplete curing of the coating in the UV curing process, then applies the electron beam radiation curing coating, and carries out the electron beam radiation curing on the two coatings, thereby obtaining the radiation curing coating with extremely excellent performance for the metal plate of the household appliance. The invention adopts components which can simultaneously adapt to two curing conditions and can fully play the roles of the two, particularly takes the resin combination of polyurethane modified epoxy acrylic resin, carbon-containing decaborane cyanate resin, multi-arm cardanol-based epoxy resin and cross-linked resin as the main material, and achieves the expected effect under the coordination of other components.
The invention adopts the polyurethane modified epoxy acrylic resin and the carbon-containing decaborane cyanate resin which are both electron beam curing prepolymers with excellent comprehensive performance, and can easily realize cross-linking polymerization with cross-linking resin after radiation so as to improve the flexibility of the coating and the adhesive force with a metal substrate.
Further, the acrylic modified polyester mentioned in the invention is acrylic modified polyester polyol resin, and according to actual needs, the acrylic modified polyester polyol resin commonly used in the market can be selected to be matched with polyurethane modified epoxy acrylic resin and carbon-containing decaborane cyanate resin for use, so as to improve the flexibility of the coating.
The invention relates to the use of cross-linking resins to increase the degree of radiation-cured cross-linking of the resin and to increase the hardness of the coating. The crosslinked resins mentioned in the present invention may be, but are not limited to, methylated melamine formaldehyde resins.
Furthermore, the polyaspartic acid ester provided by the invention can participate in a crosslinking reaction in electron beam curing to form a crosslinking network, has excellent weather resistance, particularly improves the ultraviolet resistance and corrosion resistance of the coating, improves the impact resistance of the coating, and greatly improves the repeated bending resistance of the electron beam surface coating.
The adhesion promoter is phosphate acrylate, improves the adhesion between the coating and the metal base material, is coated on the metal surface, and is not easy to fall off. In a preferred embodiment, the adhesion promoter is a phosphate methacrylate. In a more preferred embodiment, the adhesion promoter is 2-hydroxyethyl methacrylate phosphate and/or 2-hydroxyethyl methacrylate phosphate.
The active diluent adopted by the invention is one or more of 1, 6-hexanediol diacrylate, tripropylene glycol diacrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate or ditrimethylolpropane tetraacrylate. In general, the electron beam curing coating does not need a solvent, but in order to further adjust the viscosity of the electron beam curing coating, a proper amount of reactive diluent needs to be added, so that the coating is endowed with more excellent performance, the adhesion between the coating and a metal substrate and the interlayer adhesion are improved, the surface tension of the coating resin is reduced, the wettability between a resin polymer and a filler is improved, and the like.
Furthermore, the filler adopted by the invention is one or more of nano silicon dioxide, nano magnesium oxide or nano zinc oxide.
The high molecular weight polyurethane dispersant selected by the invention has the function of uniformly dispersing solid particles which are difficult to dissolve in liquid, such as fillers (nano silicon dioxide and nano magnesium oxide), and in a preferred scheme, the high molecular weight polyurethane dispersant is one or more of BYK163, RG-5160 or EFKA-4201.
The auxiliary agent is one or more of a leveling agent, a defoaming agent, a light stabilizer, an antistatic agent and an antibacterial agent; wherein the leveling agent is propylene oxide neopentyl glycol diacrylate, and the function of the leveling agent is to reduce bubbles generated in the process of preparing and using the coating. The defoaming agent is polyacrylamide, and the function of the defoaming agent is to ensure that the coating has better leveling property when being coated on the metal surface.
The invention adopts a plurality of mixed resins as main bodies, exerts the synergistic effect of the mixed resins, ensures that the coating has good hardness, flexibility and adhesive force after radiation curing in two modes, can solve the problem of poor adhesive force with a metal substrate, improves the glossiness of the coating, ensures that the coating has good adhesive force, high temperature resistance, wear resistance, weather resistance, external force scratch resistance, impact resistance, bending resistance and flexibility, particularly repeated bending resistance, can still recover the original shape and does not crack after a metal plate is subjected to larger impact deformation, and is particularly suitable for the surface of the metal substrate.
In the present invention, all the raw materials used can be obtained by commercial and/or preparative methods, which are not specifically described, and meet the requirements of standardized products.
The preparation method of the multi-arm cardanol-based epoxy resin is derived from the preparation of the multi-arm cardanol-based epoxy resin and the performance of a cured product, periodical thermosetting resin 2015-05.
The preparation method of the decaborane-containing cyanate resin is from the preparation and performance of the decaborane-containing cyanate resin and the composite material thereof in journal of Polymer science and engineering in 11 years 2018.
The preparation method of the polyaspartic acid ester is derived from Chinese invention patent with the patent number of ZL2017109706818 and the name of the preparation method of the polyaspartic acid ester.
The invention also provides a preparation method of the radiation curing coating for the metal plate of the household appliance, which comprises the following steps: and (3) respectively mixing the components of the UV radiation curing primer coating and the electron beam radiation curing surface coating, and then uniformly stirring at the temperature of 30-40 ℃.
The radiation curing coating provided by the invention can be applied to the surface of a metal plate of a household appliance, and the specific use method is as follows: coating the surface of the pretreated metal plate of the household appliance with the UV radiation curing primer, and firstly carrying out UV primary curing by an ultraviolet lamp to obtain a UV curing primer, wherein the UV curing time is below 0.4s, and the UV coating curing rate is below 80%; and after UV curing, coating the electron beam radiation curing surface layer coating on the formed semi-hardened surface bottom layer, and curing by electron beam radiation in a nitrogen environment.
In a preferred embodiment, the UV radiation-curable primer has a curing energy of 100mJ/cm when cured2The curing time is below 0.3 s; the conditions for curing the electron beam radiation curing surface coating are as follows: the radiation voltage is 380-420 KeV; the electron beam dose is 35-45 KGy; the beam current is 90-120 mA; the radiation curing temperature is 20-30 ℃, so as to form a bottom coating and a surface coating in a curing state.
The thickness of the coating applied on the surface of the household appliance metal plate can be adjusted according to the use requirement of the household appliance metal plate, and the coating thickness is 100 μm and 300 μm, for example.
Before the coating is applied to the surface of the household appliance metal plate, the surface of the household appliance metal plate is fully treated by using a sand paper polishing or sand blasting method, and then the prepared coating is coated on the surface of the household appliance metal plate after the polishing treatment by using tools such as a brush, a roller, a scraper and the like.
By adopting the technical scheme of the invention, the advantages are as follows:
the radiation curing coating for the metal plate of the household appliance provided by the invention exerts the synergistic effect of the multi-component mixed resin, and has the advantages of high coating curing efficiency, low energy consumption and environmental friendliness; meanwhile, the coating has good adhesive force, flexibility, weather resistance, impact resistance, external force scratch resistance, bending resistance and flexibility, does not crack when being bent to a certain degree, can bear the influence of repeated bending on a coating film, has smooth hand feeling, and is particularly suitable for the surface of a metal substrate.
Detailed Description
The radiation-curable coating for household electrical appliance metal sheets according to the present invention is further illustrated by the following examples, which are not intended to limit the invention in any way.
Example 1
A radiation-curable paint for the metallic plate of household appliance is composed of the UV radiation-curable primer and the electron beam radiation-curable surface paint.
The UV radiation curing primer comprises the following components in parts by weight: 45 parts of polyurethane modified epoxy acrylic resin; 40 parts of vinyl acetate; 12 parts of multi-arm cardanol epoxy resin; 12.5 parts of methylated melamine formaldehyde resin; 28 parts of a reactive diluent; 5.6 parts of an adhesion promoter; 0.6 part of carbazole ketoxime lipid photoinitiator; wherein: the active diluent is tripropylene glycol diacrylate and ethoxylated trimethylolpropane triacrylate, and the mass ratio is 1: 2; the adhesion promoter is 2-hydroxyethyl methacrylate phosphate and 2-hydroxyethyl methacrylate phosphate, and the mass ratio is 3: 2.
The electron beam radiation curing surface coating comprises the following components in parts by weight: 35 parts of polyurethane modified epoxy acrylic resin; 25 parts of carbon-containing decaborane cyanate resin; 18 parts of acrylic acid modified polyester polyol resin; 20 parts of multi-arm cardanol-based epoxy resin; 12.5 parts of cross-linked resin methylated melamine formaldehyde resin; 30 parts of a reactive diluent; 5.6 parts of an adhesion promoter; 1.8 parts of a filler; 2.7 parts of high molecular weight polyurethane dispersant; 0.9 part of an auxiliary agent;
wherein:
the active diluent is tripropylene glycol diacrylate and ethoxylated trimethylolpropane triacrylate, and the mass ratio is 1: 2;
the adhesion promoter is 2-hydroxyethyl methacrylate phosphate and 2-hydroxyethyl methacrylate phosphate, and the mass ratio is 3: 2;
the filler is nano silicon dioxide and nano magnesium oxide with the mass ratio of 1: 1;
the high molecular weight polyurethane dispersant is BYK 163;
the auxiliary agent is a leveling agent and a defoaming agent, the leveling agent is propoxylated neopentyl glycol diacrylate, the defoaming agent is polyacrylamide, and the mass ratio is 2: 1.
The UV radiation curing primer comprises the following steps: and (3) uniformly stirring the components at the temperature of 30-40 ℃.
The preparation method of the electron beam radiation curing surface coating comprises the following steps: and (3) uniformly stirring the components at the temperature of 30-40 ℃.
The weight ratio of the UV radiation curing primer to the electron beam radiation curing surface layer coating is 3: 1.
example 2
A radiation-curable paint for the metallic plate of household appliance is composed of the UV radiation-curable primer and the electron beam radiation-curable surface paint.
The UV radiation curing primer comprises the following components in parts by weight: 49 parts of polyurethane modified epoxy acrylic resin; 36 parts of vinyl acetate; 17 parts of multi-arm cardanol epoxy resin; 13.5 parts of methylated melamine formaldehyde resin; 30.8 parts of a reactive diluent; 6.8 parts of an adhesion promoter; 0.5 part of coumarin oxime ester photoinitiator; wherein: the active diluent is pentaerythritol triacrylate and ethoxylated trimethylolpropane triacrylate, and the mass ratio is 2: 1. The adhesion promoter is 2-hydroxyethyl methacrylate phosphate and 2-hydroxyethyl methacrylate phosphate, and the mass ratio is 3: 2.
The electron beam radiation curing surface coating comprises the following components in parts by weight: 40 parts of polyurethane modified epoxy acrylic resin; 25 parts of carbon-containing decaborane cyanate resin; 14.2 parts of acrylic acid modified polyester polyol resin; 22 parts of multi-arm cardanol-based epoxy resin; 13.5 parts of cross-linked resin methylated melamine formaldehyde resin; 30.8 parts of a reactive diluent; 6.8 parts of an adhesion promoter; 1.9 parts of a filler; 2.8 parts of high molecular weight polyurethane dispersant; and 1.2 parts of an auxiliary agent.
Wherein:
the active diluent is pentaerythritol triacrylate and ethoxylated trimethylolpropane triacrylate, and the mass ratio is 2: 1;
the adhesion promoter is 2-hydroxyethyl methacrylate phosphate and 2-hydroxyethyl methacrylate phosphate, and the mass ratio is 3: 2;
the filler is nano magnesium oxide and nano magnesium oxide, and the mass ratio is 1: 2;
the high molecular weight polyurethane dispersant is BYK163 and RG-5160, and the mass ratio is 1: 3;
the auxiliary agent is a leveling agent and a defoaming agent, the leveling agent is propoxylated neopentyl glycol diacrylate, the defoaming agent is polyacrylamide, and the mass ratio is 2: 1.
The above-described preparation methods of the UV radiation-curable primer coating and the electron beam radiation-curable top coating are referred to example 1. The weight ratio of the UV radiation curing primer to the electron beam radiation curing surface layer coating is 3: 1.
example 3
A radiation-curable paint for the metallic plate of household appliance is composed of the UV radiation-curable primer and the electron beam radiation-curable surface paint.
The UV radiation curing primer comprises the following components in parts by weight: 56 parts of polyurethane modified epoxy acrylic resin; 32 parts of vinyl acetate; 20 parts of multi-arm cardanol-based epoxy resin; 14.1 parts of methylated melamine formaldehyde resin; 27 parts of a reactive diluent; 5.8 parts of an adhesion promoter; 0.5 part of oxyacyl oxime ester photoinitiator; wherein: the active diluent is pentaerythritol triacrylate and tripropylene glycol diacrylate in a mass ratio of 4: 1; the adhesion promoter is 2-hydroxyethyl methacrylate phosphate and 2-hydroxyethyl methacrylate phosphate, and the mass ratio is 1: 1.
The electron beam radiation curing surface coating comprises the following components in parts by weight: 33 parts of polyurethane modified epoxy acrylic resin; 20 parts of carbon-containing decaborane cyanate resin; 12.2 parts of acrylic acid modified polyester polyol resin; 20 parts of multi-arm cardanol-based epoxy resin; 14.1 parts of cross-linked resin methylated melamine formaldehyde resin; 33 parts of a reactive diluent; 5.8 parts of an adhesion promoter; 2.4 parts of a filler; 3.1 parts of high molecular weight polyurethane dispersant; and 1.4 parts of an auxiliary agent.
Wherein:
the active diluent is pentaerythritol triacrylate and tripropylene glycol diacrylate in a mass ratio of 4: 1;
the adhesion promoter is 2-hydroxyethyl methacrylate phosphate and 2-hydroxyethyl methacrylate phosphate, and the mass ratio is 1: 1;
the filler is nano magnesium oxide and nano magnesium oxide, and the mass ratio is 3: 1;
the high molecular weight polyurethane dispersant is EFKA-4201 and RG-5160, and the mass ratio is 1: 2;
the auxiliary agent is a leveling agent and an antifoaming agent, the leveling agent is propoxylated neopentyl glycol diacrylate, the antifoaming agent is polyacrylamide, and the mass ratio is 2: 3.
The above-described preparation methods of the UV radiation-curable primer coating and the electron beam radiation-curable top coating are referred to example 1. The weight ratio of the UV radiation curing primer to the electron beam radiation curing surface layer coating is 3: 1.
example 4
A radiation-curable paint for the metallic plate of household appliance is composed of the UV radiation-curable primer and the electron beam radiation-curable surface paint.
The UV radiation curing primer comprises the following components in parts by weight: 45 parts of polyurethane modified epoxy acrylic resin; 40 parts of vinyl acetate; 12 parts of multi-arm cardanol epoxy resin; 12.5 parts of methylated melamine formaldehyde resin; 28 parts of a reactive diluent; 5.6 parts of an adhesion promoter; 0.6 part of carbazole ketoxime lipid photoinitiator; wherein: the active diluent is tripropylene glycol diacrylate and ethoxylated trimethylolpropane triacrylate, and the mass ratio is 1: 2; the adhesion promoter is 2-hydroxyethyl methacrylate phosphate and 2-hydroxyethyl methacrylate phosphate, and the mass ratio is 3: 2.
The electron beam radiation curing surface coating comprises the following components in parts by weight: 32 parts of polyurethane modified epoxy acrylic resin; 20 parts of carbon-containing decaborane cyanate resin; 7.5 parts of acrylic acid modified polyester polyol resin; 20 parts of multi-arm cardanol-based epoxy resin; 12.5 parts of cross-linked resin methylated melamine formaldehyde resin; 6.7 parts of polyaspartic acid ester; 32.5 parts of a reactive diluent; 6.6 parts of an adhesion promoter; 1.8 parts of a filler; 2.7 parts of high molecular weight polyurethane dispersant; 1.1 parts of an auxiliary agent;
wherein:
the active diluent is tripropylene glycol diacrylate and ethoxylated trimethylolpropane triacrylate, and the mass ratio is 1: 2;
the adhesion promoter is 2-hydroxyethyl methacrylate phosphate and 2-hydroxyethyl methacrylate phosphate, and the mass ratio is 3: 2;
the filler is nano silicon dioxide and nano magnesium oxide with the mass ratio of 1: 1;
the high molecular weight polyurethane dispersant is BYK 163;
the auxiliary agent is a leveling agent and a defoaming agent, the leveling agent is propoxylated neopentyl glycol diacrylate, the defoaming agent is polyacrylamide, and the mass ratio is 2: 1.
The UV radiation curing primer comprises the following steps: and (3) uniformly stirring the components at the temperature of 30-40 ℃.
The preparation method of the electron beam radiation curing surface coating comprises the following steps: and (3) uniformly stirring the components at the temperature of 30-40 ℃.
The weight ratio of the UV radiation curing primer to the electron beam radiation curing surface layer coating is 3: 1.
example 5
A radiation-curable paint for the metallic plate of household appliance is composed of the UV radiation-curable primer and the electron beam radiation-curable surface paint.
The UV radiation curing primer comprises the following components in parts by weight: 49 parts of polyurethane modified epoxy acrylic resin; 36 parts of vinyl acetate; 17 parts of multi-arm cardanol epoxy resin; 13.5 parts of methylated melamine formaldehyde resin; 30.8 parts of a reactive diluent; 6.8 parts of an adhesion promoter; 0.5 part of coumarin oxime ester photoinitiator; wherein: the active diluent is pentaerythritol triacrylate and ethoxylated trimethylolpropane triacrylate, and the mass ratio is 2: 1. The adhesion promoter is 2-hydroxyethyl methacrylate phosphate and 2-hydroxyethyl methacrylate phosphate, and the mass ratio is 3: 2.
The electron beam radiation curing surface coating comprises the following components in parts by weight: 40 parts of polyurethane modified epoxy acrylic resin; 25 parts of carbon-containing decaborane cyanate resin; 10 parts of acrylic acid modified polyester polyol resin; 24.5 parts of multi-arm cardanol epoxy resin; 14.5 parts of cross-linked resin methylated melamine formaldehyde resin; 9 parts of polyaspartic acid ester; 34.8 parts of a reactive diluent; 8.6 parts of an adhesion promoter; 1.9 parts of a filler; 3.4 parts of high molecular weight polyurethane dispersant; and 1.6 parts of an auxiliary agent.
Wherein:
the active diluent is pentaerythritol triacrylate and ethoxylated trimethylolpropane triacrylate, and the mass ratio is 2: 1;
the adhesion promoter is 2-hydroxyethyl methacrylate phosphate and 2-hydroxyethyl methacrylate phosphate, and the mass ratio is 3: 2;
the filler is nano magnesium oxide and nano magnesium oxide, and the mass ratio is 1: 2;
the high molecular weight polyurethane dispersant is BYK163 and RG-5160, and the mass ratio is 1: 3;
the auxiliary agent is a leveling agent and a defoaming agent, the leveling agent is propoxylated neopentyl glycol diacrylate, the defoaming agent is polyacrylamide, and the mass ratio is 2: 1.
The above-described preparation methods of the UV radiation-curable primer coating and the electron beam radiation-curable top coating are referred to example 1. The weight ratio of the UV radiation curing primer to the electron beam radiation curing surface layer coating is 3: 1.
example 6
A radiation-curable paint for the metallic plate of household appliance is composed of the UV radiation-curable primer and the electron beam radiation-curable surface paint.
The UV radiation curing primer comprises the following components in parts by weight: 56 parts of polyurethane modified epoxy acrylic resin; 32 parts of vinyl acetate; 20 parts of multi-arm cardanol-based epoxy resin; 14.1 parts of methylated melamine formaldehyde resin; 27 parts of a reactive diluent; 5.8 parts of an adhesion promoter; 0.5 part of oxyacyl oxime ester photoinitiator; wherein: the active diluent is pentaerythritol triacrylate and tripropylene glycol diacrylate in a mass ratio of 4: 1; the adhesion promoter is 2-hydroxyethyl methacrylate phosphate and 2-hydroxyethyl methacrylate phosphate, and the mass ratio is 1: 1.
The electron beam radiation curing surface coating comprises the following components in parts by weight: 25 parts of polyurethane modified epoxy acrylic resin; 15 parts of carbon-containing decaborane cyanate resin; 5 parts of acrylic acid modified polyester polyol resin; 15 parts of multi-arm cardanol-based epoxy resin; 8.2 parts of cross-linked resin methylated melamine formaldehyde resin; 4 parts of polyaspartic acid ester; 25 parts of a reactive diluent; 4.6 parts of an adhesion promoter; 1.4 parts of a filler; 2.2 parts of high molecular weight polyurethane dispersant; 0.6 part of an auxiliary agent. Wherein:
the active diluent is pentaerythritol triacrylate and tripropylene glycol diacrylate in a mass ratio of 4: 1;
the adhesion promoter is 2-hydroxyethyl methacrylate phosphate and 2-hydroxyethyl methacrylate phosphate, and the mass ratio is 1: 1;
the filler is nano magnesium oxide and nano magnesium oxide, and the mass ratio is 3: 1;
the high molecular weight polyurethane dispersant is EFKA-4201 and RG-5160, and the mass ratio is 1: 2;
the auxiliary agent is a leveling agent and an antifoaming agent, the leveling agent is propoxylated neopentyl glycol diacrylate, the antifoaming agent is polyacrylamide, and the mass ratio is 2: 3.
The above-described preparation methods of the UV radiation-curable primer coating and the electron beam radiation-curable top coating are referred to example 1. The weight ratio of the UV radiation curing primer to the electron beam radiation curing surface layer coating is 3: 1.
comparative example 1
The vinyl acetate in the UV radiation curable primer of example 1 was removed and the amount of urethane-modified epoxy acrylic resin was changed to 85 parts; the decaborane-containing cyanate resin in the electron beam radiation curable topcoat paint of example 1 was removed and the amount of the urethane-modified epoxy acrylic resin was changed to 55 parts, which was otherwise the same as in example 1.
Comparative example 2
The crosslinked resin in the electron beam radiation curable top coat paint of example 3 was removed and the amount of urethane-modified epoxy acrylic resin was changed to 47 parts, which was otherwise the same as in example 3.
Comparative example 3
The multi-arm cardanol-based epoxy resin in the UV radiation cured primer of example 2 was removed and the amount of urethane-modified epoxy acrylic resin was changed to 66 parts; the electron beam radiation-curable surface coating material of example 2 was removed from the multi-arm cardanol-based epoxy resin and the amount of the urethane-modified epoxy acrylic resin was changed to 62 parts, and the procedure was otherwise the same as in example 2.
Comparative example 4
The top coat was cured using only the electron beam radiation of example 1.
Comparative example 5
The primer was cured using only the UV radiation of example 1.
Comparative example 6
The acrylic modified polyester polyol resin in example 4 was removed and the amount of polyaspartic acid ester was changed to 14 parts.
Comparative example 7
The polyaspartic acid ester in example 4 was removed and the amount of the acrylic-modified polyester polyol resin was changed to 14 parts.
Example 7
The coatings prepared in examples 1-3 and comparative examples 1-5 were applied to the surface of the polished household appliance metal substrate for performance testing, and the test results are shown in table 1. The metal substrate is a 100mm x 100mm plate.
The application method comprises the following steps: coating UV radiation curing primer on the surface of the pretreated metal base material, wherein the thickness of the coating is 120 microns, carrying out UV primary curing by an ultraviolet lamp to obtain a UV semi-curing primer, coating the UV semi-curing primer with the electron beam radiation curing surface coating, and carrying out electron beam radiation curing in a nitrogen environment, wherein the thickness of the coating is 30 microns.
UV curing conditions: curing with ultraviolet lamp for 0.3s at a curing energy of 80mJ/cm2The curing rate is 80% or less.
Electron beam radiation curing conditions: curing is carried out under the conditions that the radiation voltage is 400KeV, the transmission speed of an electron accelerator is 200m/min, the beam current is 100mA, the electron beam dose is 40KGy, the nitrogen concentration is 200mg/L and the curing temperature is 25 ℃.
In which comparative example 4 was not UV-cured, the UV-curing time elongation of comparative example 5 was 5 s.
TABLE 1 relevant Performance test data for the coatings obtained
TABLE 2 relevant Performance test data for the coatings obtained
The test method and requirements are as follows:
the solid content of the coating is determined by referring to the national standard GB1725-79 coating solid content determination method.
And performing a salt spray test according to national standard GB/T10125-2012 salt spray test for artificial atmosphere corrosion test.
The impact resistance of the coatings was tested according to the national standard GB/T1732-1993 "determination of paint film impact resistance".
RCA wear resistance: abrasion resistance tester, load 175 g.
Cold and heat shock resistance: setting the high-low temperature test chamber to be placed at 60 +/-5 ℃ for 2 hours and at-25 +/-2 ℃ for 2 hours, wherein the cycle is a test after the cycle is performed; the ink coating surface of the glass does not fall off and crack, and the color of the glass is not obviously different from that of a standard sample; the specified glue, the adhesive tape and the foaming material part are stuck on the back of the coating, and the color change phenomenon can not occur when the glass is observed from the front side.
Boiling in water: decocting in water at 100 deg.C. The method comprises the following steps: the surface of the coating does not fall off or is incomplete.
Alkali resistance: soaking with 0.1M NaOH at 55 deg.C. The method comprises the following steps: the coating surface of the paint has no pinhole bubble, no expansion, no peeling, no shedding phenomenon and no color change phenomenon on the front surface.
Acid resistance: at 20 ℃ with H at a concentration of 0.05M2SO4And (5) soaking. The method comprises the following steps: the coating surface of the paint has no pinhole bubble, no expansion, no peeling, no shedding phenomenon and no color change phenomenon on the front surface.
Alcohol resistance: the test head was wrapped with cotton cloth, dipped in a qualified alcohol (concentration > 99.5%), and rubbed back and forth with 500g of pressure. The method comprises the following steps: the surface of the coating does not fall off.
Impact resistance: determined according to GB/T1732-1993 paint film impact resistance determination method.
And (3) repeated bending resistant times, namely, repeatedly bending the coating for 50 times, and observing whether the bent part is whitish, cracked or broken.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: modifications of the technical solutions described in the foregoing embodiments are still possible, or some technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A radiation curing coating for household appliance metal plates is characterized by comprising a UV radiation curing bottom coating for forming a semi-hardened surface bottom layer and an electron beam radiation curing surface coating for forming a surface hardened layer; wherein,
the UV radiation curing primer takes polyurethane modified epoxy acrylic resin, vinyl acetate, multi-arm cardanol-based epoxy resin, cross-linked resin and a photoinitiator as main materials;
the electron beam radiation curing surface layer coating mainly comprises polyurethane modified epoxy acrylic resin, carbon-containing decaborane cyanate resin, acrylic acid modified polyester, multi-arm cardanol-based epoxy resin and cross-linked resin;
the content of the electron beam radiation curing surface layer coating in the coating is below 30 percent.
2. The radiation-curable coating composition for home appliance metal plates according to claim 1, wherein the electron beam radiation-curable top coating composition further comprises polyaspartic acid ester.
3. The radiation-curable coating for household electrical appliances metal sheets according to claim 1 or 2, wherein the content of the photoinitiator in the UV radiation-curable primer is 0.5% or less.
4. The radiation-curable coating composition for home appliance metal plates as claimed in claim 1 or 2, wherein the curing time of the UV radiation-curable primer coating composition for curing is 0.4s or less, and the curing energy of the UV radiation-curable primer coating composition for curing is 100mJ/cm2The coating curing rate is below 80% for forming a semi-cured primer coating, and the coating thickness of the UV radiation curing primer coating is below 150 μm.
5. The radiation-curable coating for household electrical appliance metal plates as claimed in claim 1 or 2, wherein the conditions for curing the electron beam radiation-curable top coating are as follows: the radiation voltage is 380-420 KeV; the electron beam dose is 35-45 KGy; the beam current is 90-120 mA; the radiation curing temperature is 20-30 ℃, the bottom layer coating and the surface layer coating in a curing state are formed, and the thickness of the coating in the process of applying the electron beam radiation curing surface layer coating is less than 65 mu m.
6. The radiation-curable coating for household appliance metal plates as claimed in claim 1, wherein the UV radiation-curable primer coating comprises the following components in parts by weight: 45-60 parts of polyurethane modified epoxy acrylic resin; 30-40 parts of vinyl acetate; 10-20 parts of multi-arm cardanol-based epoxy resin; 10-20 parts of a cross-linked resin; 25-35 parts of an active diluent; 5-9 parts of an adhesion promoter; 0.2-0.7 part of photoinitiator; and the content of the photoinitiator is less than 0.5 percent.
7. The radiation-curable coating for household appliance metal plates as claimed in claim 1, wherein the electron beam radiation-curable primer coating comprises the following components in parts by weight: 25-40 parts of polyurethane modified epoxy acrylic resin; 15-25 parts of carbon-containing decaborane cyanate resin; 10-20 parts of acrylic acid modified polyester; 15-25 parts of multi-arm cardanol-based epoxy resin; 8-15 parts of a cross-linked resin; 25-35 parts of an active diluent; 4.6-8.6 parts of an adhesion promoter; 1.4-2.8 parts of a filler; 2.2-3.4 parts of high molecular weight polyurethane dispersant; 0.6-1.6 parts of an auxiliary agent.
8. The radiation-curable coating for household appliance metal plates as claimed in claim 2, wherein the electron beam radiation-curable primer coating comprises the following components in parts by weight: 25-40 parts of polyurethane modified epoxy acrylic resin; 15-25 parts of carbon-containing decaborane cyanate resin; 5-10 parts of acrylic acid modified polyester; 15-25 parts of multi-arm cardanol-based epoxy resin; 8-15 parts of a cross-linked resin; 4-9 parts of polyaspartic acid ester; 25-35 parts of an active diluent; 4.6-8.6 parts of an adhesion promoter; 1.4-2.8 parts of a filler; 2.2-3.4 parts of high molecular weight polyurethane dispersant; 0.6-1.6 parts of an auxiliary agent.
9. The radiation-curable coating for household electrical appliance metal sheets as claimed in claim 1 or 2, wherein the crosslinking resin is a methylated melamine formaldehyde resin; the acrylic modified polyester is acrylic modified polyester polyol resin; the adhesion promoter is phosphate ester acrylate, preferably phosphate ester methacrylate; more preferably 2-hydroxyethyl methacrylate phosphate and/or 2-hydroxyethyl methacrylate phosphate; the photoinitiator is oxime ester photoinitiator, preferably one or more of carbazole ketoxime lipid photoinitiator, coumarin oxime ester photoinitiator, thiophene ring dioxime photoinitiator or oxyacyl oxime ester photoinitiator; the active diluent is one or more of 1, 6-hexanediol diacrylate, tripropylene glycol diacrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate or ditrimethylolpropane tetraacrylate; the filler is one or more of nano silicon dioxide, nano magnesium oxide or nano zinc oxide; the high molecular weight polyurethane dispersant is one or more of BYK163, RG-5160 or EFKA-4201; the auxiliary agent is one or more of a leveling agent, a defoaming agent, a light stabilizer, an antistatic agent and an antibacterial agent; the auxiliary agent is a leveling agent and/or a defoaming agent; the flatting agent is propylene oxide neopentyl glycol diacrylate ester; the defoaming agent is polyacrylamide.
10. The application of the radiation curing coating for the metal plates of the household appliances to the surface of the metal plates of the household appliances, which is described in the claim 1 or the claim 2, is characterized in that the UV radiation curing primer is coated on the surface of the pretreated metal plates of the household appliances, and the UV curing primer is obtained by UV primary curing through an ultraviolet lamp, wherein the UV curing time is below 0.4s, and the curing rate of the UV coating is below 80%; and after UV curing, coating the electron beam radiation curing surface layer coating on the formed semi-hardened surface bottom layer, and curing by electron beam radiation in a nitrogen environment.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010043844.XA CN111154383A (en) | 2020-01-15 | 2020-01-15 | Radiation curing coating for household appliance metal plate and application thereof |
| CN202010043844X | 2020-01-15 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112662284A true CN112662284A (en) | 2021-04-16 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010043844.XA Withdrawn CN111154383A (en) | 2020-01-15 | 2020-01-15 | Radiation curing coating for household appliance metal plate and application thereof |
| CN202110051018.4A Withdrawn CN112662284A (en) | 2020-01-15 | 2021-01-14 | Radiation curing coating for household appliance metal plate and application thereof |
| CN202110053662.5A Pending CN112646457A (en) | 2020-01-15 | 2021-01-15 | Radiation curing coating for household appliance metal plate and application thereof |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
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| CN202010043844.XA Withdrawn CN111154383A (en) | 2020-01-15 | 2020-01-15 | Radiation curing coating for household appliance metal plate and application thereof |
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| Application Number | Title | Priority Date | Filing Date |
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| CN202110053662.5A Pending CN112646457A (en) | 2020-01-15 | 2021-01-15 | Radiation curing coating for household appliance metal plate and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111171778A (en) * | 2020-01-15 | 2020-05-19 | 王超 | Radiation mother-son plate curing colloid and forming method of daughter plate thereof |
| CN114773560B (en) * | 2022-04-22 | 2023-11-21 | 深圳飞扬骏研新材料股份有限公司 | Preparation method of salt spray resistant modified polyaspartic acid ester, salt spray resistant modified polyaspartic acid ester and coating |
| CN115948093B (en) * | 2022-11-18 | 2023-10-17 | 广东希贵光固化材料有限公司 | UVLED white primer for aluminum pinch plate and application thereof |
| CN115948111A (en) * | 2022-12-09 | 2023-04-11 | 中创新航科技股份有限公司 | Photocuring coating and battery comprising same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102167948B (en) * | 2011-02-25 | 2013-08-28 | 上海长润发涂料有限公司 | UV (ultraviolet) photo-cured acrylic resin composition |
| CN102898878B (en) * | 2012-10-23 | 2015-09-30 | 上海乘鹰新材料有限公司 | Electron beam radiation cured coating of low cost, high adhesive force and preparation method thereof |
| CN106433258B (en) * | 2016-09-30 | 2018-09-04 | 南京工程学院 | A kind of metal heavy-duty electron beam radiation curable coating |
-
2020
- 2020-01-15 CN CN202010043844.XA patent/CN111154383A/en not_active Withdrawn
-
2021
- 2021-01-14 CN CN202110051018.4A patent/CN112662284A/en not_active Withdrawn
- 2021-01-15 CN CN202110053662.5A patent/CN112646457A/en active Pending
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| CN112646457A (en) | 2021-04-13 |
| CN111154383A (en) | 2020-05-15 |
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Application publication date: 20210416 |