Coating material for metal substrate based on photocurable composition

Abstract

The invention discloses a coating for a metal substrate based on a photocurable composition, which comprises a primer layer, a finishing coat layer and a varnish layer which are sequentially arranged from bottom to top, and the primer layer, the finishing coat layer and the varnish layer jointly form the coating for the metal substrate; the primer layer, the finish paint layer and the varnish layer are all based on a composition comprising ethyl carbamate acrylic resin, a polymerizable monomer, a photoinitiator, a filler, an anticorrosive pigment, a pigment, a dispersing agent, a defoaming agent, a flowable agent, a rheological additive, a functional additive, an adhesion promoter, an antioxidant and a light stabilizer. The adhesive force of the coating to various metal substrates is improved, the corrosion resistance and weather resistance of the coating are improved, the content of dry slag in the coating is increased, the hardness, strength and flexibility of the coating are improved, the total thickness of the coating can reach 150 micrometers when the coating is formed through light curing, and therefore the coating with various colors and luster can be obtained.

Description

Technical Field

[0001] The present invention relates to the technical field of industrial coatings, such as coil coatings, can coatings and anti-corrosion coatings, and in particular to a coating for metal substrates based on a photocurable composition. Background Art

[0002] Coatings based on compositions comprising photosensitive oligomeric resins, acrylic monomers, organic and inorganic pigments and fillers, accelerators, and adjuvants are known. Disadvantages of these coatings include the need for expensive electron beam (EB) equipment to cure the compositions and insufficient corrosion protection. [Patent CN108977047, published on November 12, 2018]

[0003] Known coatings are based on photocurable compositions comprising a dissolved monomer, a photoinitiator, and a promoter for adhesion to metal. Disadvantages of these compositions include a low curing rate and a low level of adhesive interaction between the coating and the metal substrate. Furthermore, the composition requires a buffer solution, which has a limited shelf life and contributes to its low manufacturability [Patent CN109321011, published on February 12, 2019].

[0004] Known coatings based on photocurable compositions include resins and monomers, photoinitiators, pigments, matting agents, adhesion promoters, and additives. Coatings derived from these compositions suffer from insufficient lightfastness, weathering resistance, and corrosion resistance, as well as difficulty in forming coatings thicker than 25 microns [US Patent WO2005108344A1, published on November 16, 1984].

[0005] The closest solution to the proposed invention (prototype) is a coating based on a photocurable composition comprising epoxy acrylate, acrylated blocked isocyanate, monoacrylate, and polypropylene. Disadvantages of coatings made with this composition are a low level of adhesive interaction with the metal substrate and insufficient light resistance during operation due to the use of epoxy acrylate [Patent US4481258. Issued on November 16, 1984]. Summary of the Invention

[0006] To address the aforementioned technical problems of the prior art, the present invention provides a coating for metal substrates based on a photocurable composition. The coating formed by the present invention can be applied at a thickness of up to 150 microns while exhibiting high adhesion to various metal substrates, high corrosion resistance, and weather resistance. This coating improves the adhesion level of the coating to various metal substrates, increases the hardness and flexibility of the coating, and can be applied at a total thickness of up to 150 microns when formed using photocuring.

[0007] The technical solution adopted in the present invention is:

[0008] A coating for a metal substrate based on a photocurable composition, characterized in that it comprises a primer layer, a topcoat layer and a clearcoat layer arranged in sequence from bottom to top, wherein the primer layer, the topcoat layer and the clearcoat layer together form the coating for the metal substrate;

[0009] The three paint layers of the primer layer, the topcoat layer and the clearcoat layer are all based on a composition including urethane acrylic resin, polymerizable monomers, photoinitiators, fillers, anticorrosive pigments, pigments, dispersants, defoamers, flow agents, rheological additives, functional additives, adhesion promoters, antioxidants and light stabilizers.

[0010] Furthermore, the primer layer is composed of the following components in parts by weight:

[0011] Polyurethane acrylic resin: 20-60 parts

[0012] Polymerizable monomer: 20-60 parts

[0013] Photoinitiator: 3-15 parts

[0014] Anticorrosive pigment: 1-15 parts

[0015] Filling agent: 0-20 parts

[0016] Pigment: 0-20 parts

[0017] Dispersant: 0.1-3.0 parts

[0018] Deoxidizer: 0.1-3.0 parts

[0019] Defoaming agent: 0.1-3.0 parts

[0020] Flow agent: 0.1-3.0 parts

[0021] Rheological additive: 0.01-3.00 parts

[0022] Functional additives: 0.01-3.00 parts Adhesion promoter: 0.1-10.0 parts Matting agent: 0.001-10,000 parts;

[0023] The topcoat layer is composed of the following components in parts by weight: polyurethane acrylic resin: 20-60 parts

[0024] Polymerizable monomer: 20-60 parts

[0025] Photoinitiator: 3-15 parts

[0026] Filling agent: 0-20 parts

[0027] Pigment: 0-50 parts

[0028] Dispersant: 0.1-3.0 parts

[0029] Deoxidizer: 0.1-3.0 parts

[0030] Defoaming agent: 0.1-3.0 parts

[0031] Flow agent: 0.1-3.0 parts

[0032] Rheological additive 0.01-3.00 parts

[0033] Functional additives: 0.01-3.00 parts

[0034] Adhesion promoter: 0.1-10.0 parts

[0035] Matting agent: 0.001-10,000 parts

[0036] Antioxidant: 0.01-3.00 parts

[0037] Light stabilizer: 0.01-3.00 parts;

[0038] The varnish layer is composed of the following components in parts by weight:

[0039] Polyurethane acrylic resin: 20-60 parts

[0040] Polymerizable monomer: 20-60 parts

[0041] Photoinitiator: 3-15 parts

[0042] Pigment: 0-15 parts

[0043] Dispersant: 0.1-3.0 parts

[0044] Deoxidizer: 0.1-2.0 parts

[0045] Defoaming agent: 0.1-2.0 parts

[0046] Flow agent: 0.1-3.0 parts

[0047] Rheological additive: 0.01-3.00 parts

[0048] Functional additives: 0.01-3.00 parts

[0049] Adhesion promoter: 0.1-10.0 parts

[0050] Matting agent: 0.001-10,000 parts

[0051] Antioxidant: 0.01-3.00 parts

[0052] Light stabilizer: 0.01-3.00 parts.

[0053] Furthermore, in the primer layer, the polyurethane acrylic resin adopts PRO33118 brand urethane acrylic resin or PRO33555 brand urethane acrylic resin; in the topcoat layer and the clearcoat layer, the polyurethane acrylic resin adopts ST991NS resin or CN790NS resin.

[0054] Furthermore, the polymerizable monomer includes isobornyl acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, 1,6-hexanediol diacrylate, 2-hydroxypropyl methacrylate, OTA-480 brand glyceryl triacrylate, trimethylolpropane triacrylate, methacrylic acid, neopentyl glycol diacrylate, pentaerythritol tetraacrylate, 2-hydroxyethyl methacrylate or ethoxylated pentaerythritol tetraacrylate.

[0055] Furthermore, the photoinitiator includes 1-hydroxycyclohexyl phenyl ketone (184), diphenyl-(2,4,6-trimethylbenzoyl)-phosphine oxide (TPO), ethylphenyl-(2,4,6-trimethylbenzoyl)-phosphinate (TPO-L), 2-isopropylthioxanthenone (ITX), 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one (907), and 2-hydroxy-2-methylhydroquinone (1173).

[0056] Furthermore, the anticorrosive pigments include zinc phosphate, Heucophos SRPP, Shieldex C303, Shieldex CS311, Finntalc M05N-SQ, NOVINOX XCA02, NCF-140, NCF-160, NSC-230, NSC-280, NSC-500, zap, zop, zpm, zatp, catp, zpam, Zpasc, Zpc or its analogues.

[0057] Furthermore, the fillers are micronized and non-micronized organic and inorganic fillers;

[0058] The pigments are organic and inorganic pigments;

[0059] The dispersant is DISPERBYK-2009, DISPERBYK-164, DISPERBYK-2013, DISPERBYK-168, EFKA-4010, Solsperse 86000 or the like;

[0060] The diluent is XL6507, XL6531 or similar;

[0061] The defoamer is BYK-053, BYK-054, BYK-055, BYK-057, BYK-088, BYK-1790 or the like;

[0062] The filler is Allnex 1360, 350 or similar;

[0063] The rheological additive is RHEOBYK-405, AEROSIL 200, AEROSIL 300, AEROSIL R805, AEROSIL R812S, AEROSIL R972 or the like;

[0064] The filling agent is micronized talc Talc SR, micronized barium sulfate Blanc Fix Micro or micronized kaolin Argical M-1000.

[0065] Furthermore, the adhesion promoter is prepared by the following method:

[0066] The adhesion promoter is obtained by mixing the following components at a temperature of 25-40° C. and a mixing speed of 500-1000 rpm:

[0067] Products based on a mixture of 85% orthophosphoric acid solution (CAS 7664-38-2) and CN9051NS trifunctional ester in a ratio of 10:1 to 1:10;

[0068] Based on 85% orthophosphoric acid solution (CAS 7664-38-2) and b-302 products of a mixture of acrylic acid esters in a ratio of 10:1 to 1:1;

[0069] Products based on a mixture of an 85% solution of orthophosphoric acid (CAS 7664-38-2) and an epoxy resin in a ratio of 10:1 to 1:10;

[0070] Based on 85% orthophosphoric acid solution (CAS 7664-38-2) and 168 products in a mixture ratio of 10:1 to 1:1;

[0071] Products based on a mixture of 85% orthophosphoric acid (CAS 7664-38-2) and linear polyester Tech 7255 having active hydrogen atoms in a ratio of 10:1 to 1:10;

[0072] Products based on a mixture of 85%-orthophosphoric acid (CAS7664-38-2) and trimethoxymethylsiloxane Tech7005 in a ratio of 10:1 to 1:10;

[0073] Products based on a mixture of 85%-orthophosphoric acid (CAS7664-38-2) and vinyltrimethoxysilane Tech7004 in a ratio of 10:1 to 1:10;

[0074] Products based on a mixture of 85%-orthophosphoric acid (CAS7664-38-2) and ethyl silicate Tech7002 in a ratio of 10:1 to 1:10 respectively;

[0075] Products based on a mixture of 85%-orthophosphoric acid (CAS7664-38-2) and oligomeric ethyl silicate Tech7002-2 in a ratio of 10:1 to 1:10;

[0076] Products based on a mixture of 85% orthophosphoric acid solution (CAS 7664-38-2) and tetramethylorthosilicate Tech 7001 in a ratio of 10:1 to 1:10;

[0077] Products based on a mixture of 85% orthophosphoric acid solution (CAS 7664-38-2) and the acid group-bearing polyester composition Tech 7763 in a ratio of 10:1 to 1:10;

[0078] Products based on a mixture of 85% orthophosphoric acid solution (CAS 7664-38-2) and an organic phosphorus composition having unsaturated groups Tech 7145 in a ratio of 10:1 to 1:10;

[0079] Products based on a mixture of 85% orthophosphoric acid solution (CAS 7664-38-2) and Tech 7135, an organic silicone composition having epoxy groups, in a ratio of 10:1 to 1:10;

[0080] Products based on a mixture of 85% orthophosphoric acid solution (CAS 7664-38-2) and Tech 7125, an organic silicone composition having epoxy groups, in a ratio of 10:1 to 1:10;

[0081] Products based on a mixture of 85% orthophosphoric acid solution (CAS 7664-38-2) and a silicone composition having amine groups of Tech 7121 in a ratio of 10:1 to 1:10;

[0082] Products based on a mixture of 85% orthophosphoric acid solution (CAS 7664-38-2) and modified polyester Tech 7063 in a ratio of 10:1 to 1:10;

[0083] Products based on a mixture of 85% orthophosphoric acid solution (CAS 7664-38-2) and Tech 7040, an organic silicone composition having epoxy groups, in a ratio of 10:1 to 1:10;

[0084] Products based on a mixture of 85% orthophosphoric acid (CAS 7664-38-2) and Tech 7030, an organosilicon composition having methyl acrylate groups, in a ratio of 10:1 to 1:10;

[0085] Products based on a mixture of an 85% solution of 85% orthophosphoric acid (CAS 7664-38-2) and an organophosphorus composition of an unsaturated group of Tech 7146 in a ratio of 10:1 to 1:10;

[0086] Products based on a mixture of 85% orthophosphoric acid (CAS 7664-38-2) and an organophosphorus composition having unsaturated groups, Tech 7063, in a ratio of 10:1 to 1:10;

[0087] Or products based on a mixture of 85% orthophosphoric acid (CAS 7664-38-2) and modified polyester Tech 7300 in a ratio of 10:1 to 1:10.

[0088] The technical concept of the present invention is:

[0089] The essence of the present invention is the formation of a photocurable three-layer coating, each layer performing specific functions. The primer layer provides reliable adhesion to the metal substrate and the corrosion protection of the entire three-layer coating. The primer layer composition achieves a balance of adhesion, corrosion protection, and physical and mechanical properties. The functional binder-active groups of the polyurethane-acrylic resin ensure high adhesion strength of the coating to the metal substrate. The molecular weight characteristics of these resins result in a regular network structure with a narrow molecular weight distribution between the chains in the coating material. The use of selected polymerizable monomers enables an optimal combination of strength and flexibility due to a balance of flexible and rigid polymer chain segments. The combination of photoinitiators with different absorption peaks in the composition results in a broad absorption band for the photoinitiator mixture, which increases the conversion depth of the functional groups and forms a spatial structure with increased crosslinking density, regardless of the physicochemical properties of the pigments and fillers used. The adhesion promoter used simultaneously activates the metal substrate surface to increase the effectiveness of the formation of adhesion-active centers during the interaction between the reactive groups of the resins and monomers included in the composition and the metal substrate surface to be painted, and forms additional chemical bonds with the metal surface in the coating due to the presence of adhesion-active groups in the promoter. The functional additives in the proposed composition perform several tasks: they improve the wettability and effectiveness of dyeing the metal substrate surface by reducing the wetting edge angle and reduce the coating's sensitivity to scratches and stains. The use of the polyurethane acrylic resin, polymerizable monomers, antioxidants and stabilizers proposed in the present invention determines the high weather resistance of the coating.

[0090] Compared with the prior art, the beneficial effects of the present invention are embodied in:

[0091] The coating formed by the present invention can have a thickness of up to 150 microns and at the same time have a high level of adhesion to various metal substrates, high corrosion protection and weather resistance, increase the adhesion level of the coating to various metal substrates, increase the hardness and flexibility of the coating, and can be applied with a total thickness of up to 150 microns when using light curing to form the coating. BRIEF DESCRIPTION OF THE DRAWINGS

[0092] Figure 1 This is the infrared spectrum of the used polyurethane acrylic resin of the PRO33118 brand;

[0093] Figure 2 This is the chromatogram of used polyurethane acrylic resin of the PRO33118 brand;

[0094] Figure 3 This is the infrared spectrum of the used polyurethane acrylic resin of the PRO33555 brand;

[0095] Figure 4 This is the infrared spectrum of the used urethane acrylic resin grade CN991NS;

[0096] Figure 5 It is a chromatogram of Cn991NS brand polyurethane acrylic resin;

[0097] Figure 6 is the infrared spectrum of the trifunctional ether used;

[0098] Figure 7 is used Infrared spectrum of b-302 acrylate. DETAILED DESCRIPTION

[0099] The following describes the specific implementation of the embodiment of the present invention in detail with reference to the accompanying drawings. It should be understood that the specific implementation described herein is only used to illustrate and explain the embodiment of the present invention and is not used to limit the embodiment of the present invention.

[0100] It should be noted that, in the absence of conflict, the embodiments of the present invention and the features therein may be combined with each other.

[0101] The present invention will be described in detail below with reference to the accompanying drawings and in conjunction with exemplary embodiments.

[0102] For the manufacture of the composition, mixing and dispersing equipment was used to ensure that the solid particles in the composition were not more than 25 microns in size.

[0103] In order to facilitate the adjustment of the color, decorative properties, technical and operating properties of coatings, prefabricated pigment pastes, premixes and semi-finished products are used in the production of paints and varnishes. Paints and varnishes are prepared by mixing and dispersing the following components: polyurethane acrylic resins, polymerization monomers, photoinitiators, anticorrosive pigments, fillers, pigments, dispersants, defoamers, extenders, rheological additives, functional additives, adhesion promoters, matting additives that reduce the gloss of the coating.

[0104] The radiation energy used is 1200-2000MJ / cm 2 (UVA), 200-700MJ / cm 2 (UVB), 200-500MJ / cm 2 (UVC), 1200-1600MJ / cm 2 The composition is cured by a UV radiation source such as a mercury lamp (UVV).

[0105] The metal substrates to be coated include hot-dip galvanized steel, electro-galvanized steel, tin-plated steel, copper-plated steel, carbon steel, stainless steel, aluminum, alloys, etc. in the form of coils or sheets.

[0106] The composition and properties of the compositions and coatings are given in Tables 1 and 2.

[0107] The primer layer composition was prepared according to the following method, and 123.12 kg was finally obtained. The specific process is as follows:

[0108] 37.6 kg of PRO33555 brand polyurethane acrylic resin, 17.4 kg of 1,6-hexanediol diacrylate, and 2 kg of ota-480 brand glyceryl triacrylate were added to a thermostatically controlled bowl equipped with a milling cutter, belt and scraper mixer to mix, disperse and achieve the desired grinding, pigment paste, premix and semi-finished product. Trimethylol triacrylate, 1 kg of methacrylic acid, 2 kg of neopentyl glycol diacrylate, 1 kg of pentaerythritol tetraacrylate, 4.7 kg of 1-hydroxycyclohexyl phenyl ketone (184). 2.2 kg of diphenyl-(2,4,6-trimethylbenzoyl)-phosphine oxide (TPO), 1.4 kg of ethylphenyl-(2,4,6-trimethylbenzoyl)-phosphonate (TPO-L), 1 kg of Heucophos SRPP, 1 kg of NCF-160, 5 kg of NSC-500, 2 kg ZAP, 2kg ZATP, 1kg micronized barium sulfate Blanc Fix Micro, 2kg micronized Argic M-1000 kaolin, 30kg tiona828, 0.01kg pg645, 0.9kg byk-168, 0.3kg Efka-4010, 0.5kg xl6507,0.5kg byk-057,0.2kg Byk-1790,0.2Kg 350, 0.05KG Rheobyk-405, 0.01kg aerosil r972, 0.01kg mixture of polyfluorinated telomer alcohols, 0.01kg 1h, 1h, 11h-trihydrofluorodecyl stearate, 1kg 85% orthophosphoric acid solution, 0.1kg 85% orthophosphoric acid solution and mixture of CN9051NS trifunctional ester, 0.1kg 85% orthophosphoric acid solution and acrylate-302 mixed orthophosphoric acid and oligomeric ethyl silicate TECH7002-2, 0.01 kg deuteron mm669. The composition was applied to a plate made of electrogalvanized steel and 6 painted plates were prepared to obtain statistically reliable data on the coating properties. The radiation energy used was 1560 MJ / cm 2 (UVA), 520MJ / cm 2 (UVB), 430MJ / cm 2 (UVC), 1300MJ / cm 2 The composition for the primer layer was cured using a UV radiation source of a mercury lamp (UVV). The composition for facial enamel was applied to the primer layer.

[0109] The composition of the glaze layer was prepared according to the following method, and 129.3 kg was finally obtained. The specific process is as follows:

[0110] In a thermostatically controlled bowl equipped with a milling cutter, belt and scraper mixer were added 40 kg of CN991NS urea resin, 3.6 kg of CN790NS urea resin, 25 kg of 1,6-hexanediol diacrylate, 2 kg of glyceryl triacrylate OTA-480, 1 kg of trimethylol triacrylate to prepare the pigment paste, premix and semi-finished product, 1 kg of methacrylic acid, 2 kg of neopentyl glycol diacrylate, 1 kg of pentaerythritol tetraacrylate, 4.7 kg of 1-hydroxycyclohexyl benzophenone (184), 3.0 kg of diphenyl-(2,4,6-trimethylbenzoyl)-phosphine oxide (TPO), 1.8 kg of ethylphenyl-(2,4,6-trimethylbenzoyl)-phosphonate (TPO-L), 1.5 kg of micronized talc, 5 kg of micronized barium sulfate Blanc Fix Micro, 2 kg of micronized kaolin Argical M-1000, 30 kg of Tiona828, 0.01kg PG645, 0.9kg DISPERBYK-168, 0.3kgefka-4010, 0.5kg xl6507, 0.5kg byk-057, 0.2kg byk-1790, 0.2KG 350, 0.05 kg rheobyk-405, 0.01 kg aerosil r972, 0.01 kg polyfluorinated alcohol-telomer mixture, 0.01 kg 1h, 1h, 11h-trihydrofluorodecyl stearate, 1 kg 85% orthophosphoric acid solution, 1 kg mixture of 85% orthophosphoric acid solution and CN9051NS trifunctional ester, 1 kg 85% orthophosphoric acid solution and A mixture of B-302 acrylate, 0.7 kg of 85% orthophosphoric acid solution and 168 of vinyltrimethoxysilane Tech 7004 was applied to panels made of electrogalvanized steel and six painted panels were prepared to obtain statistically reliable data on the coating properties. Radiant energy of 1560 MJ / cm 2 (UVA), 520MJ / cm 2 (UVB), 430MJ / cm 2 (UVC), 1300MJ / cm 2 The composition is cured using a UV radiation source from a mercury lamp (UVV). The composition for the clearcoat layer is applied to the layer of front enamel.

[0111] The composition of the varnish layer was prepared according to the following method, and 92.2 kg was finally obtained. The specific process is as follows:

[0112] In a thermostatically controlled bowl equipped with a milling cutter, belt and scraper mixer were added 40 kg of CN991NS urea resin, 3.6 kg of CN790NS urea resin, 25 kg of 1,6-hexanediol diacrylate, 2 kg of glyceryl triacrylate OTA-480, 1 kg of trimethylol triacrylate to prepare pigment pastes, premixes and semi-finished products, 1 kg of methacrylic acid, 2 kg of neopentyl glycol diacrylate, 1 kg of pentaerythritol tetraacrylate, 4.7 kg of 1-hydroxycyclohexylbenzophenone (184), 3.0 kg of diphenyl-(2,4,6-trimethylbenzoyl)-phosphine oxide (TPO), 1.8 kg of ethylphenyl-(2,4,6-trimethylbenzoyl)-phosphonate (TPO-L), 3 kg of Tiona828, 0.01 kg of PG645, 0.9 kg of BYK-168, 0.3 kg of EFKA-4010, 0.5 kg of XL6507, 0.2kg byk-1790, 0.2kg 350, 0.05kg rheobyk-405, 0.01kg aerosil r972, 0.01KG polyfluorinated alcohol-telomere mixture, 0.01kg 1h, 1h, 11H-trihydrofluorodecyl stearate, 1kg 85% orthophosphoric acid solution, 0.1kg, 0.1kg orthophosphoric acid and A mixture of an 85% solution of b-302 acrylate, 0.7 kg of orthophosphoric acid and an 85% solution of vinyltrimethoxysilane Tech 7004, 0.7 kg of orthophosphoric acid and oligomeric ethyl silicate Tech 7002-2 was applied to a panel made of electrogalvanized steel, and 6 painted panels were prepared to obtain statistically reliable data on the coating properties. The composition was cured using a mercury lamp UV radiation source with radiation energies of 1560 MJ / cm2 (UVA), 520 MJ / cm2 (UVB), 430 MJ / cm2 (UVC), and 1300 MJ / cm2 (UVV).

[0113] The coating properties were measured according to the test standards shown in Table 2. Similarly, compositions were prepared according to Examples 2-15 in Table 1. Specifically,

[0114] 37 kg of epoxy acrylate, 10 kg of an acrylated blocked isocyanate based on toluene diisocyanate and 2-hydroxyethyl acrylate, 0.1 kg of benzoquinone, 14 kg of polyacrylate, 54 kg of trimethylolpropane triacrylate, and 0.1 kg of Vicure 10 were placed in a thermostatically controlled bowl equipped with a milling cutter, a belt mixer, and a scraper mixer. The composition was applied to electrogalvanized steel panels, forming three layers in sequence for an equivalent comparison with the proposed invention. Six painted panels were prepared to obtain statistically reliable data on the coating properties. The composition was cured layer by layer using a mercury lamp UV radiation source with radiant energies of 1560 MJ / cm2 (UVA), 520 MJ / cm2 (UVB), 430 MJ / cm2 (UVC), and 1300 MJ / cm2 (UVV).

[0115] The coating properties were measured according to the test standards shown in Table 2, as follows:

[0116] When the content of the urethane acrylic resin is less than 20% by weight, the coating's elastic strength, substrate adhesion, corrosion resistance, and weather resistance are reduced. Increasing the content of the urethane acrylic resin to more than 60% by weight results in an increase in viscosity and a decrease in the manufacturability of the composition.

[0117] When the content of the polymerizable monomer is less than 20% by weight, h. elastic strength and adhesion of the coating to the substrate are reduced, and the manufacturability of the composition deteriorates. When the content of the urethane acrylic resin is greater than 60% by weight, h. T-bend and adhesion of the coating to the substrate are reduced.

[0118] When the photoinitiator content is less than 3 wt %, the coating's elasticity, strength, adhesion to the substrate, corrosion resistance, and weather resistance are reduced. When the photoinitiator content exceeds 15 wt %, the photoinitiator overspending results in decreased elasticity, strength, and adhesion to the substrate.

[0119] When the content of the anticorrosive pigment is less than 1% by weight, the anticorrosive performance of the coating is reduced. Increasing the content of the anticorrosive pigment to more than 15% by weight results in an overabundance of the anticorrosive pigment, which reduces the processability, elastic strength properties, and adhesion of the coating to the substrate of the coating composition.

[0120] An increase in pigment content above 20 wt. % h. results in a decrease in the manufacturability, elastic strength properties, adhesion of the coating to the substrate, and interlayer adhesion of the composition.

[0121] An increase in filler content above 20 wt. h. results in a decrease in the processability of the applied composition, elastic strength properties, adhesion of the coating to the substrate and interlayer adhesion.

[0122] When the dispersant content is less than 0.1 wt %, the grinding degree and sedimentation stability of the composition, elastic strength properties, adhesion of the coating to the substrate, and interlayer adhesion are reduced. Increasing the dispersant content to more than 3 wt % leads to over-spending of the dispersant, which reduces elastic strength properties, adhesion of the coating to the substrate, and interlayer adhesion.

[0123] When the dispersant content is less than 0.1 wt %, foaming increases during the composition manufacturing process, pore formation in the coating, and the number of surface defects increases. Increasing the dispersant content above 3 wt % results in over-spreading of the dispersant, decreased elastic strength properties, and decreased adhesion of the coating to the substrate and interlayer adhesion.

[0124] When the defoamer content is less than 0.1 wt %, foaming during the composition manufacturing process increases, pore formation in the coating, and the number of surface defects increases. Increasing the defoamer content above 3 wt % results in over-branching of the dispersant, decreased elastic strength properties, and decreased adhesion of the coating to the substrate and interlayer adhesion.

[0125] When the rheological additive content is less than 0.01 wt. %, runoff from vertical surfaces increases and the wear resistance of the composition deteriorates. Increasing the rheological additive content above 3 wt. % results in decreased manufacturability of the composition, over-branching of the dispersant, decreased elastic strength properties, and poor adhesion of the coating to the substrate and interlayer adhesion.

[0126] When the content of functional additives is less than 0.01 wt%, the effectiveness of coloring the metal substrate and the antifouling and anti-vandal properties of the coating are reduced. Increasing the content of functional additives above 3 wt% results in a decrease in elastic strength, T-bend, adhesion of the coating to the substrate, and interlayer adhesion.

[0127] When the content of adhesion promoter is less than 0.1wt%, the adhesion of the coating to the substrate and the interlayer adhesion, the corrosion resistance and weather resistance of the coating are reduced. Increasing the content of adhesion promoter above 10wt% will lead to excessive expansion of the adhesion promoter, reduction of elastic strength properties, T-bending, adhesion of the coating to the substrate and interlayer adhesion.

[0128] When the content of matting additive is less than 0.001 wt%, the gloss of the coating increases. Increasing the content of matting additive above 10 wt% results in a decrease in elastic strength properties, T-bend, adhesion of the coating to the substrate, and interlayer adhesion.

[0129] When the antioxidant content is less than 0.01 wt %, the weather resistance of the coating decreases. Increasing the antioxidant content above 3 wt % results in a decrease in the composition's manufacturability, elastic strength properties, T-bend properties, adhesion of the coating to the substrate, and interlayer adhesion.

[0130] When the light stabilizer content is less than 0.01 wt. h., the weather resistance of the coating decreases. Increasing the light stabilizer content to more than 3 wt. h. results in a decrease in the manufacturability, elastic strength properties, T-bend properties, adhesion of the coating to the substrate, and interlayer adhesion of the composition.

[0131] In summary, the coating proposed by the present invention has increased adhesion levels to various metal substrates, improved corrosion resistance and weather resistance, increased hardness, strength and flexibility, can be formed into a coating by photocuring, and can apply a coating with a total thickness of up to 150 microns.

[0132] refer to Figures 1 to 7 , PRO33118 brand urethane acrylic resin and PRO33555 brand urethane acrylic resin were used as the urethane acrylic resin for the primer layer.

[0133] PRO33118 resin manufactured by Sartomer (Arkema) has the following characteristics:

[0134]

[0135] PRO33555 resin manufactured by Sartomer (Arkema) has the following characteristics:

[0136]

[0137] CN991NS resin and CN790NS resin were used as polyurethane acrylic resins for topcoat and clearcoat layers.

[0138] CN991NS resin manufactured by Sartomer (Arkema) has the following characteristics:

[0139] Appearance: transparent liquid

[0140] Viscosity at 25°C, MPa*s (centipoise) 6000-12000

[0141] Color (APHA) 0-100

[0142] CN790NS resin manufactured by Sartomer (Arkema) has the following characteristics:

[0143]

[0144] The functional additive was prepared in the following manner (an industrial product was used according to specification 301-14-1-89 (Technical Condition 301-14-1-89)):

[0145] The product of the polyfluoro telomer alcohol mixture synthesized by the free radical mechanism of telomerization of tetrafluoroethylene in methanol is as follows:

[0146] H(CF2CF2)nCH2OH

[0147] Where n = 4-8;

[0148] Industrial product consisting of a mixture of a product based on an 85% solution of orthophosphoric acid and a mixture of the above-mentioned polyfluorotelomer alcohols (Technical Conditions 301-14-1-89)

[0149] H(CF2CF2)nCH2OH, where n=4-8.

[0150] The oligomerization product 1',1',11,'-trihydrofluorodecyloxy-(2"-hydroethyl)-oligo-2-methyl-1-oxyene (density p = 1267 kg / m 3 and surface tension σ=28.3mn / m 2 ), obtained by the reaction of propylene oxide with 1h,1H,11H-trihydrofluorodecanol-1, the general formula is

[0151]

[0152] The synthesis of 1',1',11,'-trihydrofluorodecyloxy-(2"-hydroethyl)-oligo-2-methyl-1-oxyalkylene was carried out according to the standard method of adding propylene oxide to alcohol. [MS Malinovsky. Olefin oxides and their derivatives. Moscow: 1951. p. 552]. 100 parts by mass of 1,1,11-trihydrofluorodecanol was charged to a reactor, followed by the addition of a proton-donor catalyst in an amount of 0.1-0.5 mass percent based on the weight of the alcohol. Air was pumped out using a water jet pump. The reactor is heated to a residual pressure of 30-50 mmHg. The reaction mixture is then heated to 80-90°C while stirring to produce an alcohol melt. The required amount of propylene oxide is supplied to the reactor via a bubbler. The polyaddition reaction of propylene oxide is carried out at 90–120°C and an excess pressure of 1.2-1.5 atm. During polymerization, strong absorption of propylene oxide occurs. At the end of the reaction, the temperature is lowered to 80-90°C and residual propylene oxide is blown off with nitrogen while the gas mixture is pumped through with a water jet pump.

[0153] The product 1',1',11,'-trihydrofluorodecyloxy-(2"-hydroethyl)-oligo-2-methyl-1-oxoolefin (density p=1267 kg / m) was prepared from a mixture of 85% orthophosphoric acid solution (CAS 7664-38-2) and oligomeric products. 3 and surface tension σ=28.3mn / m 2 ), obtained by the reaction of propylene oxide with 1h,1H,11H-trihydrofluorodecanol-1, the general formula is

[0154]

[0155] 1h,1h-perfluoroheptyloxysilane (boiling point Tc = 106-1080C / 38mm, density p = 1.5044 g / cm 3 Surface tension σ=22.3mN / m 2 ), obtained by the interaction of epichlorohydrin with 1h,1h-dihydrotrifluoroheptanol-1 [US Patent 3,849,401, published 19.11.1974], with the formula:

[0156]

[0157] Based on orthophosphoric acid (CAS 7664-38-2) and 1h,1h-perfluoroheptyloxysilane (boiling point Tc = 106-1080C / 38mm, density p = 1.5044 g / cm 3 Surface tension σ=22.3mN / m 3 ) by the interaction of epichlorohydrin with 1H,1H-dihydridecafluoroheptanol-1 [U.S. Patent 3,849,401, published 19.11.1974], having the general formula

[0158]

[0159] Stearate is 1H,1H,11H-trihydrofluorooctanol (softening temperature in the temperature range of Traz. = 60-80 ° C), obtained by esterification of stearic acid with 1H,1H,11H-trihydrofluorodecanol [USSR Copyright Certificate No. 729173, published 04 / 08 / 1980], having the general formula

[0160]

[0161] The product is based on a mixture of 85% orthophosphoric acid solution (CAS 7664-38-2) and 1H,1H,11H-trihydrofluorodecyl stearate (softening temperature in the temperature range of 60-80°C).

[0162]

[0163] Table 1 Composition of the composition

[0164]

[0165]

[0166]

[0167]

[0168]

[0169]

[0170]

[0171]

[0172]

[0173]

[0174]

[0175]

[0176]

[0177]

[0178]

[0179]

[0180]

[0181]

[0182]

[0183] Table 2 Coating properties

[0184]

[0185]

[0186]

[0187]

[0188]

[0189]

[0190] Although the embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and are not to be construed as limitations on the present invention. A person skilled in the art may change, modify, replace and modify the above embodiments within the scope of the present invention.

Claims

1. A coating for a metal substrate based on a photocurable composition, characterized in that: The invention comprises a primer layer, a topcoat layer and a clearcoat layer arranged in sequence from bottom to top, wherein the primer layer, the topcoat layer and the clearcoat layer together form a coating for a metal substrate; The three paint layers of the primer layer, the topcoat layer and the clearcoat layer are all based on a composition including urethane acrylic resin, polymerizable monomers, photoinitiators, fillers, anticorrosive pigments, pigments, dispersants, defoamers, flow agents, rheological additives, functional additives, adhesion promoters, antioxidants and light stabilizers.

2. A coating for a metal substrate based on a photocurable composition according to claim 1, characterized in that: The primer layer is composed of the following components in parts by weight: Polyurethane acrylic resin: 20-60 parts Polymerizable monomer: 20-60 parts Photoinitiator: 3-15 parts Anticorrosive pigment: 1-15 parts Filling agent: 0-20 parts Pigment: 0-20 parts Dispersant: 0.1-3.0 parts Deoxidizer: 0.1-3.0 parts Defoaming agent: 0.1-3.0 parts Flow agent: 0.1-3.0 parts Rheological additive: 0.01-3.00 parts Functional additives: 0.01-3.00 parts Adhesion promoter: 0.1-10.0 parts Matting agent: 0.001-10,000 parts; The topcoat layer is composed of the following components by weight: polyurethane acrylic resin: 20-60 parts polymerizable monomer: 20-60 parts Photoinitiator: 3-15 parts Filling agent: 0-20 parts Pigment: 0-50 parts Dispersant: 0.1-3.0 parts Deoxidizer: 0.1-3.0 parts Defoaming agent: 0.1-3.0 parts Flow agent: 0.1-3.0 parts Rheological additive 0.01-3.00 parts Functional additives: 0.01-3.00 parts Adhesion promoter: 0.1-10.0 parts Matting agent: 0.001-10,000 parts Antioxidant: 0.01-3.00 parts Light stabilizer: 0.01-3.00 parts; The varnish layer is composed of the following components in parts by weight: polyurethane acrylic resin: 20-60 parts polymerizable monomer: 20-60 parts Photoinitiator: 3-15 parts Pigment: 0-15 parts Dispersant: 0.1-3.0 parts Deoxidizer: 0.1-2.0 parts Defoaming agent: 0.1-2.0 parts Flow agent: 0.1-3.0 parts Rheological additive: 0.01-3.00 parts Functional additives: 0.01-3.00 parts Adhesion promoter: 0.1-10.0 parts Matting agent: 0.001-10,000 parts Antioxidant: 0.01-3.00 parts Light stabilizer: 0.01-3.00 parts.

3. A coating for a metal substrate based on a photocurable composition according to claim 2, characterized in that: In the primer layer, the polyurethane acrylic resin adopts PRO33118 brand urethane acrylic resin or PRO33555 brand urethane acrylic resin; in the topcoat layer and the clearcoat layer, the polyurethane acrylic resin adopts ST991NS resin or CN790NS resin.

4. A coating for a metal substrate based on a photocurable composition according to claim 2, characterized in that: The polymerizable monomers include isobornyl acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, 1,6-hexanediol diacrylate, 2-hydroxypropyl methacrylate, OTA-480 brand glyceryl triacrylate, trimethylolpropane triacrylate, methacrylic acid, neopentyl glycol diacrylate, pentaerythritol tetraacrylate, 2-hydroxyethyl methacrylate or ethoxylated pentaerythritol tetraacrylate.

5. The coating for metal substrates based on a photocurable composition according to claim 2, characterized in that: The photoinitiator includes 1-hydroxycyclohexyl phenyl ketone (184), diphenyl-(2,4,6-trimethylbenzoyl)-phosphine oxide (TPO), ethylphenyl-(2,4,6-trimethylbenzoyl)-phosphinate (TPO-L), 2-isopropylthioxanthenone (ITX), 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one (907), and 2-hydroxy-2-methylhydroquinone (1173).

6. A coating for a metal substrate based on a photocurable composition according to claim 2, characterized in that: The anticorrosive pigments include zinc phosphate, Heucophos SRPP, Shieldex C303, Shieldex CS311, Finntalc M05N-SQ, NOVINOX XCA02, NCF-140, NCF-160, NSC-230, NSC-280, NSC-500, or its analogues.

7. A coating for a metal substrate based on a photocurable composition according to claim 2, characterized in that: The fillers are micronized and non-micronized organic and inorganic fillers; The pigments are organic and inorganic pigments; The dispersant is DISPERBYK-2009, DISPERBYK-164, DISPERBYK-2013, DISPERBYK-168, EFKA-4010, Solsperse 86000 or the like; The diluent is or similar; The defoamer is BYK-053, BYK-054, BYK-055, BYK-057, BYK-088, BYK-1790 or the like; The filler is Allnxin or similar; The rheological additive is RHEOBYK-405, AEROSIL 200, AEROSIL 300, AEROSIL R805, AEROSIL R812S, AEROSIL R972 or the like; The filling agent is micronized talc Talc SR, micronized barium sulfate Blanc Fix Micro or micronized kaolin Argical M-1000.

8. The coating for metal substrates based on a photocurable composition according to claim 2, wherein: The adhesion promoter is obtained by mixing the following components at a temperature of 25-40° C. and a mixing speed of 500-1000 rpm: Products based on a mixture of 85% orthophosphoric acid solution (CAS 7664-38-2) and CN9051NS trifunctional ester in a ratio of 10:1 to 1:10; Based on 85% orthophosphoric acid solution (CAS 7664-38-2) and Products containing mixtures of acrylic acid esters in a ratio of 10:1 to 1:1; Products based on a mixture of an 85% solution of orthophosphoric acid (CAS 7664-38-2) and an epoxy resin in a ratio of 10:1 to 1:10; Based on 85% orthophosphoric acid solution (CAS 7664-38-2) and 168 products in a mixture ratio of 10:1 to 1:1; Products based on a mixture of 85% orthophosphoric acid (CAS 7664-38-2) and linear polyester Tech 7255 having active hydrogen atoms in a ratio of 10:1 to 1:10; Products based on a mixture of 85%-orthophosphoric acid (CAS7664-38-2) and trimethoxymethylsiloxane Tech7005 in a ratio of 10:1 to 1:10; Products based on a mixture of 85%-orthophosphoric acid (CAS7664-38-2) and vinyltrimethoxysilane Tech7004 in a ratio of 10:1 to 1:10; Products based on a mixture of 85%-orthophosphoric acid (CAS7664-38-2) and ethyl silicate Tech7002 in a ratio of 10:1 to 1:10 respectively; Products based on a mixture of 85%-orthophosphoric acid (CAS7664-38-2) and oligomeric ethyl silicate Tech7002-2 in a ratio of 10:1 to 1:10; Products based on a mixture of 85% orthophosphoric acid solution (CAS 7664-38-2) and tetramethylorthosilicate Tech 7001 in a ratio of 10:1 to 1:10; Products based on a mixture of 85% orthophosphoric acid solution (CAS 7664-38-2) and the acid group-bearing polyester composition Tech 7763 in a ratio of 10:1 to 1:10; Products based on a mixture of 85% orthophosphoric acid solution (CAS 7664-38-2) and an organic phosphorus composition having unsaturated groups Tech 7145 in a ratio of 10:1 to 1:10; Products based on a mixture of 85% orthophosphoric acid solution (CAS 7664-38-2) and Tech 7135, an organic silicone composition having epoxy groups, in a ratio of 10:1 to 1:10; Products based on a mixture of 85% orthophosphoric acid solution (CAS 7664-38-2) and Tech 7125, an organic silicone composition having epoxy groups, in a ratio of 10:1 to 1:10; Products based on a mixture of 85% orthophosphoric acid solution (CAS 7664-38-2) and a silicone composition having amine groups of Tech 7121 in a ratio of 10:1 to 1:10; Products based on a mixture of 85% orthophosphoric acid solution (CAS 7664-38-2) and modified polyester Tech 7063 in a ratio of 10:1 to 1:10; Products based on a mixture of 85% orthophosphoric acid solution (CAS 7664-38-2) and Tech 7040, an organic silicone composition having epoxy groups, in a ratio of 10:1 to 1:10; Products based on a mixture of 85% orthophosphoric acid (CAS 7664-38-2) and Tech 7030, an organosilicon composition having methyl acrylate groups, in a ratio of 10:1 to 1:10; Products based on a mixture of an 85% solution of 85% orthophosphoric acid (CAS 7664-38-2) and an organophosphorus composition of an unsaturated group of Tech 7146 in a ratio of 10:1 to 1:10; Products based on a mixture of 85% orthophosphoric acid (CAS 7664-38-2) and an organophosphorus composition having unsaturated groups, Tech 7063, in a ratio of 10:1 to 1:10; Or products based on a mixture of 85% orthophosphoric acid (CAS 7664-38-2) and modified polyester Tech 7300 in a ratio of 10:1 to 1:10.

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