Matte excimer UV-curable anti-graffiti composition, coating containing the same, and preparation method of the coating

Abstract

The present invention discloses a matte excimer UV-curable anti-graffiti composition, a coating containing the same, and a preparation method of the coating. The matte excimer UV-curable anti-graffiti composition comprises the following components: 30 to 60 parts by weight of a hyperbranched organosilicon-modified polyurethane acrylate resin, 30 to 60 parts by weight of an active diluent monomer, and 1 to 6 parts by weight of a photoinitiator; the functionality of the hyperbranched organosilicon-modified polyurethane acrylate resin is 4 to 20; the functionality of the active diluent monomer is ≥3. The matte excimer UV-curable anti-graffiti coating obtained by the present invention has a large crosslinking degree, obvious surface shrinkage after curing by the excimer technology, excellent matte effect, and the organopolysiloxane segments contained therein are basically non-crystalline, endowing the coating with good flexibility and anti-fouling and anti-graffiti effects.

Description

Technical Field

[0001] The present invention belongs to the technical field of excimer UV curing, and particularly relates to a matte excimer UV curing anti-graffiti composition, a coating containing the same, and a preparation method of the coating. Background Art

[0002] The excimer curing technology is a technology that uses an excimer lamp to emit short-wave ultraviolet light with a wavelength of 170 - 175 nm to irradiate a UV curing coating, so that the coating cures only on the surface, while the interior of the coating does not cure. By using excimer curing, the surface of the UV coating can be polymerized and crosslinked, and shrinkage occurs to form a non-smooth surface, thereby achieving the effects of surface matte and skin touch.

[0003] For example, Patent CN115806769A discloses an excimer UV coating material and a preparation method thereof. The excimer UV coating material includes bisphenol A epoxy acrylate, succinic acid, acrylic acid, triphenylphosphine, 4-methoxyphenol, aliphatic polyurethane acrylate, active diluent, defoamer, leveling agent, photoinitiator, dispersant, organic filler, rheology aid, and matting agent.

[0004] Patent CN115433481A discloses a composition and a preparation method of a 170 - 175 nm excimer UV skin-friendly and temperature-resistant floor coating. The excimer UV skin-friendly and temperature-resistant floor coating consists of fluorosilicon-modified acrylate resin, active diluent, photoinitiator, matting powder, wear-resistant powder, and additives, etc.

[0005] The above-mentioned excimer UV coatings still need to add fillers such as organic fillers and matting agents to increase the matte, wear-resistant, anti-fouling, and skin-touch effects. However, adding these fillers will affect the crosslinking density, flexibility, and hand feeling of the coating, resulting in the coating being difficult to achieve better anti-graffiti performance, flexibility, and hand feeling.

[0006] Therefore, developing an anti-graffiti coating that can achieve a better matte effect without adding a matting agent and has better anti-fouling and anti-graffiti effects, flexibility, and hand feeling is a technical problem to be solved in this field. Summary of the Invention

[0007] Aiming at the deficiencies of the prior art, the purpose of the present invention is to provide a matte excimer UV curing anti-graffiti composition, a coating containing the same, and a preparation method of the coating. The matte anti-graffiti coating cured by the matte excimer UV curing anti-graffiti composition can achieve a better matte effect without adding matte powder, and has better anti-graffiti performance and flexibility.

[0008] To achieve this purpose, the present invention adopts the following technical solutions:

[0009] In a first aspect, the present invention provides a matte excimer UV-curable anti-graffiti composition.

[0010] A matte excimer UV-curable anti-graffiti composition, in parts by weight, the matte excimer UV-curable anti-graffiti composition comprises the following components: 30 to 60 parts by weight of hyperbranched silicone-modified polyurethane acrylate resin (such as 32 parts by weight, 34 parts by weight, 36 parts by weight, 38 parts by weight, 40 parts by weight, 42 parts by weight, 44 parts by weight, 46 parts by weight, 48 parts by weight, 50 parts by weight, 52 parts by weight, 54 parts by weight, 56 parts by weight, 58 parts by weight, etc.), 30 to 60 parts by weight of reactive diluent monomer (such as 32 parts by weight, 34 parts by weight, 36 parts by weight, 38 parts by weight, 40 parts by weight, 42 parts by weight, 44 parts by weight, 46 parts by weight, 48 parts by weight, 50 parts by weight, 52 parts by weight, 54 parts by weight, 56 parts by weight, 58 parts by weight, etc.) and 1 to 6 parts by weight of photoinitiator;

[0011] The functionality of the hyperbranched silicone-modified polyurethane acrylate resin is 4 to 20; for example, it can be 5-functional, 6-functional, 7-functional, 8-functional, 9-functional, 10-functional, 11-functional, 12-functional, 13-functional, 14-functional, 15-functional, 16-functional, 17-functional, 18-functional, 19-functional, etc.

[0012] The functionality of the reactive diluent monomer is ≥3; for example, it can be 4-functional, 5-functional, 6-functional, 7-functional, 8-functional, etc.

[0013] The inventors of the present invention have found through research that the crosslinking degree of the coating has a great influence on the matte effect of the excimer UV-cured coating. By selecting a hyperbranched silicone-modified polyurethane acrylate resin with high functionality as the main resin, on the one hand, the hyperbranched structure endows it with the characteristics of low viscosity and high activity. By using it in combination with a highly functional reactive diluent monomer, it has a higher shrinkage rate, and it is not necessary to add a matting agent. Only through the excimer UV-curing technology can an excellent matte effect be achieved on the coating surface; on the other hand, the molecular chain segment of the highly functional hyperbranched silicone-modified polyurethane acrylate resin contains a silicone chain segment, so that the obtained coating can have flexibility while having a very high crosslinking density, thereby making the obtained coating have excellent anti-graffiti property, stain resistance, wear resistance and hand feeling.

[0014] Preferably, the structural general formula of the hyperbranched silicone-modified polyurethane acrylate resin is selected from any one or a combination of polymers shown in the following structural general formulas;

[0015]

[0016] Each R1 is independently selected from any one of substituted or unsubstituted C1-C20 straight-chain or branched-chain alkyl, substituted or unsubstituted phenyl, and hydroxyl;

[0017] Each R2 and each R3 are each independently selected from a polyureaurethane or polyurethane residue obtained by reacting an amino group or a hydroxyl group with an isocyanate group;

[0018] Each R4 is independently selected from a polymerization chain segment residue of an unsaturated end-capped monomer and an isocyanate group, and has 1-5 carbon-carbon double bonds; the chain segment at the end of the R4 has 1-5 carbon-carbon double bonds;

[0019] Each R5 is independently selected from any one of a substituted or unsubstituted C1-C20 straight-chain or branched-chain alkylene group, a substituted or unsubstituted C6-C20 arylene group, a substituted or unsubstituted C6-C15 cycloalkylene group, and -Ar1-L-Ar2-.

[0020] The hyperbranched organosilicon-modified polyurethane acrylate resin used in the present invention has a polyurethane residue grafted with organosilicon as a branching center, and finally has multiple carbon-carbon unsaturated double bonds as an outer shell. The obtained hyperbranched organosilicon-modified polyurethane acrylate resin not only has better mechanical properties, flexibility and compatibility, but also has better adhesion and anti-graffiti properties.

[0021] Preferably, the hyperbranched organosilicon-modified polyurethane acrylate resin can be prepared by the following steps:

[0022] S1. React an isocyanate group-terminated organosilicon prepolymer with an amino polyol containing at least one secondary amino group to obtain a multi-hydroxy-terminated branching center A;

[0023] S2. React the multi-hydroxy-terminated branching center A with a polyisocyanate to obtain an isocyanate group-terminated prepolymer B;

[0024] S3. React the isocyanate group-terminated prepolymer B obtained in step S2 with an unsaturated end-capped monomer. After the reaction is completed, the hyperbranched organosilicon photosensitive resin is obtained.

[0025] Preferably, in step S1, the molar ratio between the NCO group in the isocyanate group-terminated organosilicon prepolymer and the secondary amino group in the amino polyol is 1:(1-1.05).

[0026] Preferably, in step S2, the molar ratio between the hydroxyl group in the core prepolymer and the NCO group in the polyisocyanate is 1:(2-2.05).

[0027] Preferably, in step S3, the molar ratio between the NCO group in the isocyanate group-terminated prepolymer and the hydroxyl group in the hydroxyl group-containing unsaturated end-capped monomer is 1:(1-1.05).

[0028] Preferably, in step S1, the temperature of the reaction is 0 to 5 °C, for example, it can be 1 °C, 2 °C, 3 °C, 4 °C, etc.

[0029] Preferably, in step S1, the reaction time is 30 to 60 min.

[0030] Preferably, in step S2, the reaction time is 1 to 3 hours.

[0031] Preferably, in step S2, the reaction temperature is 60 to 90 °C.

[0032] Preferably, in step S3, the reaction time is 1 to 3 hours.

[0033] Preferably, in step S3, the reaction temperature is 60 to 90 °C.

[0034] Preferably, the amino polyol includes one or more of diethanolamine, dipropanolamine, diisopropanolamine, 2-amino-1,3-propanediol, 3-amino-1,2-propanediol, and dibutanolamine.

[0035] Preferably, the unsaturated capping monomer includes one or more of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, pentaerythritol triacrylate, and dipentaerythritol pentaacrylate.

[0036] Preferably, the polyisocyanate includes toluene diisocyanate (TDI), methylcyclohexyl diisocyanate (HTDI), 4,4'-diphenylmethane diisocyanate (MDI), 4,4'-dicyclohexylmethane diisocyanate (HMDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), and a mixture of one or two of its homologues, derivatives, and isomers.

[0037] Preferably, the isocyanate group-terminated polysiloxane can be selected from commercially available products, such as one or more of Silok3062F2, Silok3067F2, Silok3023F2, and Silok3073F2 of Guangzhou Slok Polymer Co., Ltd.

[0038] Preferably, the hyperbranched organosilicon-modified polyurethane acrylate resin can also be purchased from commercially available products, and examples include Silok 3826F2, Silok 3826F4, Silok 3826F5, Silok 3826F16, and Silok 3826F20 of Guangzhou Slok Polymer Co., Ltd.

[0039] Preferably, the reactive diluent is one or more of trimethylolpropane triacrylate (TMPTA), trimethylolpropane trimethacrylate (TMPTMA), pentaerythritol triacrylate (PETA), pentaerythritol tetraacrylate (PETTA), bis-trimethylolpropane tetraacrylate (Di-TMPTA), ditrimethylolpropane tetraacrylate (DTEMATTA), dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate.

[0040] By selecting reactive diluent monomers with a higher functionality, the present invention, together with the main resin with a high functionality, provides a higher curing rate, crosslinking density, and shrinkage rate. After curing using excimer technology, a better matte effect and anti-graffiti and anti-fouling effects can be achieved.

[0041] Preferably, the photoinitiator includes one or more of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (TPO), phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (819), 2-hydroxy-2-methyl-1-phenyl-1-propanone (1173), 2-methyl-1-[4-(methylthio)phenyl]-2-morpholin-1-propanone (907), and 1-hydroxy-cyclohexyl-phenylmethanone (184).

[0042] Preferably, by weight, the matte excimer UV-curable anti-graffiti composition further includes 0 to 2 parts of a photosensitizer.

[0043] Preferably, the photosensitizer is one or more of triethanolamine, N,N-dimethylethanolamine, N,N-dimethylaniline, and ethyl 4-(N,N-dimethylamino)benzoate.

[0044] Preferably, by weight, the matte excimer UV-curable anti-graffiti composition further includes 0.3 - 0.5 parts by weight of a wetting and dispersing agent and 0 to 0.5 parts by weight of an antifoaming agent.

[0045] Preferably, the wetting and dispersing agent includes an organopolysiloxane containing isocyanate groups and carboxyl groups.

[0046] Preferably, the wetting and dispersing agent includes Silok3072M2 of Guangzhou Slok Polymer Co., Ltd.

[0047] The wetting and dispersing agent used in the present invention is an organopolysiloxane containing isocyanate groups and carboxyl groups. The inventor of the present invention has found that for the wetting and dispersing agent with such a structure, its silicone main chain can provide excellent wetting and leveling effects. At the same time, it has isocyanate groups, has excellent compatibility with the main resin, and can react with the active groups hydroxyl and amino of the main resin, while the carboxyl groups can provide better emulsifying and dispersing properties. Compared with other types of wetting agents or dispersing agents, the wetting and dispersing agent used in the present invention has both wetting and leveling properties, dispersibility and reactivity, and has better compatibility with the main resin.

[0048] Preferably, the defoaming agent comprises a mixture of modified silicone and silica.

[0049] Preferably, the defoaming agent comprises one or more of Silok 4010, Silok 4013, Silok 4016, and Silok 4019 of Guangzhou Slok Polymer Co., Ltd.

[0050] The defoaming agent used in the present invention is applicable to an oil-based system, has a stronger defoaming effect, and better defoaming efficiency.

[0051] In a second aspect, the present invention provides an application of the matte excimer UV-curable anti-graffiti composition as described in the first aspect in an excimer UV-curable coating or an excimer UV-curable ink.

[0052] In a third aspect, the present invention provides a matte excimer UV-curable anti-graffiti coating, which contains the matte excimer UV-curable anti-graffiti composition as described in the first aspect.

[0053] In a fourth aspect, the present invention provides a preparation method of the matte excimer UV-curable anti-graffiti coating as described in the third aspect.

[0054] The preparation method includes the following steps: after coating the matte excimer UV-curable anti-graffiti composition on the surface of a substrate, surface curing is carried out using an ultraviolet excimer lamp, and after completing the surface curing, deep curing is carried out using an ultraviolet lamp to obtain the matte excimer UV-curable anti-graffiti coating.

[0055] The above-mentioned ultraviolet excimer lamp is a light source lamp that can emit a single 172 nm ultraviolet ray. Compared with a conventional ultraviolet lamp, the ultraviolet ray emitted by it has a shorter wavelength and a narrower wavelength range.

[0056] Specifically, ultraviolet lamps can include mercury lamps, xenon lamps, gallium lamps, LED lamps, etc.

[0057] Preferably, the step of deep curing is: first curing using an LED lamp, and then curing using a mercury lamp, a xenon lamp or a gallium lamp.

[0058] Compared with the prior art, the present invention has the following beneficial effects:

[0059] 1. The present invention uses a high-rank hyperbranched organosilicon-modified polyurethane acrylate resin as the main resin and a high-rank active diluent in combination. The obtained matte excimer UV-curable anti-graffiti coating has a large crosslinking degree, and after curing by the excimer technology, the surface shrinkage is obvious, and it has an excellent matte effect. This hyperbranched organosilicon-modified polyurethane acrylate resin contains an organopolysiloxane chain segment that is basically non-crystalline. Compared with polyester or polyether modified toughening monomers, the introduction of the organosilicon chain segment enables the resin to balance crosslinking degree, curing speed and flexibility, and has a higher toughening efficiency, overcoming the defects of brittle and hard paint film and insufficient impact resistance caused by high crosslinking degree. In addition, the organosilicon chain segment itself has a relatively low polarity and weak stain adhesion. Coupled with the fact that the crosslinking density of the cured coating itself is large enough, the coating has good anti-fouling and anti-graffiti effects. At the same time, the organosilicon has a good lubricating feeling, and the organosilicon chain segment has a tendency to enrich on the surface, which can just provide the unique smooth feeling of organosilicon.

[0060] 2. The main resin used in the present invention is a hyperbranched organosilicon-modified polyurethane acrylate resin, which has good compatibility with other components, and the obtained paint film is transparent. This is because after the organosilicon molecule is incorporated into the polyurethane group and allophanate group, its compatibility with acrylic monomers is greatly increased, and the foggy white phenomenon caused by directly adding organosilicon monomers will not occur.

[0061] 3. The hyperbranched organosilicon-modified polyurethane acrylate resin used in the present invention itself has a tertiary amine structure, which has an effect of inhibiting oxygen inhibition of polymerization. Therefore, in the case of a large amount of hyperbranched organosilicon-modified polyurethane acrylate resin, it can be cured in air without nitrogen protection. At the same time, it can be cured with little or no addition of tertiary amine photosensitizer without being affected by oxygen inhibition of polymerization. This is more conducive to 170-175nm excimer photocuring, thus overcoming the defect that traditional excimer curing requires curing under nitrogen protection. Detailed implementation mode

[0062] The technical solution of the present invention will be further described below through specific implementation modes. Those skilled in the art should understand that the described embodiments are only for helping to understand the present invention and should not be regarded as specific limitations on the present invention. Unless otherwise specified, the "parts" and "%" in the following embodiments are "parts by weight" and "wt%", respectively, and the raw materials and methods used are all conventional raw materials and methods in the art.

[0063] The raw materials used in the embodiments of the present invention can all be obtained through public channels, and the information of the manufacturers of some raw materials is as follows:

[0064] The hyperbranched organosilicon modified polyurethane acrylate resin is Silok 3826F2 (4-functional), Silok 3826F4 (4-functional), Silok 3826F5 (6-functional), Silok 3826F16 (16-functional), Silok 3826F20 (20-functional) of Guangzhou Silok Polymer Co., Ltd.;

[0065] Wetting and dispersing agent: an organopolysiloxane containing isocyanate groups and carboxyl groups, specifically Silok 3072M2 of Guangzhou Silok Polymer Co., Ltd.

[0066] Example 1

[0067] A matte excimer UV-curable anti-graffiti composition comprises the following components:

[0068] 60 g of hyperbranched organosilicon modified polyurethane acrylate resin Silok 3826F5 (functionality of 6-functional), 20 g of trimethylolpropane triacrylate, 14.6 g of dipentaerythritol pentaacrylate, 3 g of photoinitiator TPO, 2 g of photoinitiator 1173, 0.3 g of wetting and dispersing agent Silok 3072M2, 0.1 g of defoaming agent Silok4010.

[0069] The preparation method of the above matte excimer UV-curable anti-graffiti composition is as follows:

[0070] Put the above components into a stirring kettle, shear and disperse at a speed of 800 rpm for 15 min to obtain the matte excimer UV-curable anti-graffiti composition.

[0071] The preparation method of the matte excimer UV-curable anti-graffiti coating is as follows:

[0072] Coat the above matte excimer UV-curable anti-graffiti composition on the surface of a PC board, and then perform surface curing with excimer UV light of 170 - 175 nm. After the surface curing is completed, perform deep curing with LED-UV light of 395 nm wavelength, and finally perform ultraviolet deep curing with a double mercury lamp to obtain the matte excimer UV-curable anti-graffiti coating (B1).

[0073] Example 2

[0074] A matte excimer UV-curable anti-graffiti composition comprises the following components:

[0075] 40 g of hyperbranched organosilicon modified polyurethane acrylate resin Silok 3826F2 (functionality of 4-functional), 27.2 g of trimethylolpropane trimethacrylate, 30 g of dipentaerythritol hexaacrylate, 1 g of photoinitiator 819, 0.3 g of wetting and leveling agent 3072M2, 1.5 g of photosensitizer N,N-dimethylaniline.

[0076] The preparation method of the above matte excimer UV-curable anti-graffiti composition is as follows:

[0077] Put the above components into a stirring kettle, shear and disperse at a speed of 900 rpm for 30 min, and obtain the matte excimer UV-curable anti-graffiti composition.

[0078] The preparation method of the matte excimer UV-curable anti-graffiti coating includes the following steps: After coating the above matte excimer UV-curable anti-graffiti composition on the surface of a PC board, perform surface curing with excimer UV light of 170-175 nm. After completing the surface curing, perform deep curing with LED-UV light with a wavelength of 395 nm, and finally perform ultraviolet deep curing with a gallium lamp to obtain the matte excimer UV-curable anti-graffiti coating (B2).

[0079] Example 3

[0080] A matte excimer UV-curable anti-graffiti composition includes the following components:

[0081] 50 g of hyperbranched organosilicon-modified polyurethane acrylate resin Silok 3826F16 (functionality of 16), 42 g of pentaerythritol triacrylate, 6 g of photoinitiator 1173, 0.5 g of wetting and leveling agent 3072M2, 1 g of photosensitizer triethanolamine, 0.5 g of defoaming agent 4010.

[0082] The preparation method of the above matte excimer UV-curable anti-graffiti composition is as follows:

[0083] Put the above components into a stirring kettle, shear and disperse at a speed of 1000 rpm for 20 min, and obtain the matte excimer UV-curable anti-graffiti composition.

[0084] The preparation method of the matte excimer UV-curable anti-graffiti coating includes the following steps:

[0085] After coating the above matte excimer UV-curable anti-graffiti composition on the surface of a PC board, perform surface curing with excimer UV light of 170-175 nm. After completing the surface curing, perform deep curing with LED-UV light with a wavelength of 395 nm, and finally perform ultraviolet deep curing with a gallium lamp, xenon lamp or double mercury lamp to obtain the matte excimer UV-curable anti-graffiti coating (B3).

[0086] Example 4

[0087] A matte excimer UV-curable anti-graffiti composition includes the following components:

[0088] 32 g of hyperbranched silicone-modified polyurethane acrylate resin Silok 3826F2 (functionality of 4), 60 g of pentaerythritol tetraacrylate, 5.5 g of photoinitiator 907, 0.3 g of wetting and leveling agent 3072M2, 2 g of photosensitizer N,N-dimethylethanolamine, 0.2 g of defoaming agent 4010.

[0089] The preparation method of the above matte excimer UV-curable anti-graffiti composition is as follows:

[0090] Put the above components into a stirring kettle, and shear and disperse them at a rotation speed of 1000 rpm for 20 min to obtain a matte excimer UV-curable anti-graffiti composition.

[0091] A preparation method of a matte excimer UV-curable anti-graffiti coating includes the following steps:

[0092] After coating the above matte excimer UV-curable anti-graffiti composition on the surface of a PC board, perform surface curing with excimer UV light of 170 - 175 nm. After completing the surface curing, perform deep curing with LED-UV light of a wavelength of 395 nm, and finally perform ultraviolet deep curing with a xenon lamp to obtain the matte excimer UV-curable anti-graffiti coating (B4).

[0093] Example 5

[0094] A matte excimer UV-curable anti-graffiti composition includes the following components:

[0095] 50 g of hyperbranched silicone-modified polyurethane acrylate resin Silok 3826F20 (functionality of 20), 45 g of ditrimethylolpropane tetraacrylate, 4 g of photoinitiator 184, 0.3 g of wetting and leveling agent 3072M2, 0.5 g of photosensitizer ethyl 4-(N,N-dimethylamino)benzoate, 0.2 g of defoaming agent 4010.

[0096] The preparation method of the above matte excimer UV-curable anti-graffiti composition is as follows:

[0097] Put the above components into a stirring kettle, and shear and disperse them at a rotation speed of 1000 rpm for 20 min to obtain a matte excimer UV-curable anti-graffiti composition.

[0098] A preparation method of a matte excimer UV-curable anti-graffiti coating includes the following steps:

[0099] After coating the above matte excimer UV-curable anti-graffiti composition on the surface of the PC board, surface curing is carried out using excimer UV light of 170-175 nm. After completing the surface curing, deep curing is carried out using LED-UV light with a wavelength of 395 nm, and finally, ultraviolet deep curing is carried out using a gallium lamp, xenon lamp or double mercury lamp to obtain the matte excimer UV-curable anti-graffiti coating (B5).

[0100] Comparative Example 1

[0101] The hyperbranched organosilicon-modified polyurethane acrylate resin used in this comparative example is basically the same as the method (PFS-1) disclosed in CN115433481A, except that perfluorodecyl acrylate is not added during the preparation process.

[0102] The other components of this comparative example are the same as those in Example 1, and the matte excimer UV-curable anti-graffiti coating (B6) is prepared by the same preparation method as in Example 1.

[0103] Comparative Example 2

[0104] The difference between this comparative example and Example 1 is that the reactive diluent monomer dipentaerythritol pentaacrylate is replaced with the same weight of tripropylene glycol diacrylate (TPGDA).

[0105] The other components of this comparative example are the same as those in Example 1, and the matte excimer UV-curable anti-graffiti coating (B7) is prepared by the same preparation method as in Example 1.

[0106] Performance Test:

[0107] 1. Perform performance tests on the gloss, anti-graffiti property, abrasion resistance, gloss and smoothness of the matte excimer UV-curable anti-graffiti coatings (B1-B7) obtained in Examples 1-5 and Comparative Examples 1-2, and the test results are shown in Table 1. The test methods are as follows:

[0108] (1) Anti-graffiti property: After scribbling on the surface of the above matte excimer UV-curable anti-graffiti coating with an oil-based marker pen, wipe it with a dry cloth and evaluate according to the remaining situation of the marks after wiping. The evaluation results are set as 2-5 points, where 5 points represent easy to wipe without leaving marks, 4 points represent easy to wipe with a small amount of marks left, 3 points represent can be wiped with marks left, and 2 points represent difficult to wipe with marks left.

[0109] (3) Gloss: In accordance with the national standard GB / T 9754-2007 "Determination of 20°, 60° and 85° Specular Gloss of Paints and Varnishes - Paints without Metallic Pigments".

[0110] (4) Smoothness: Evaluate the feel of the matte excimer UV-curable anti-graffiti coating. According to the smoothness, it is rated from 2 to 5 points, where 5 points represent the best smoothness, close to the feel of the skin; 2 points represent poor smoothness.

[0111] 2. Scrape the matte excimer UV-curable anti-graffiti coatings obtained in Examples 1 to 5 and Comparative Examples 1 to 2 onto tinplate test samples. After surface curing with excimer UV light of 170 - 175 nm, then perform deep curing with LED-UV light of 395 nm wavelength, and finally perform ultraviolet deep curing with a double mercury lamp. The obtained coating films are determined according to the national standard GB / T 1731-2020 "Determination Method for Flexibility of Paint Films and Putty Films".

[0112] Table 1

[0113]

[0114] In the present invention, by using a high-generation hyperbranched organosilicon-modified polyurethane acrylate resin as the main resin and combining it with a high-generation active diluent, the obtained matte excimer UV-curable anti-graffiti coating has a high crosslinking degree. After curing by the excimer technology, the surface shrinkage is obvious, with an excellent matte effect, and at the same time has good flexibility and anti-graffiti properties.

[0115] By comparing Example 1 with Comparative Example 2, it can be seen that when the functionality of the active diluent monomer used is relatively low, a better matte effect cannot be achieved.

[0116] The applicant declares that the present invention is illustrated by the above examples, but the present invention is not limited to the above examples, that is, it does not mean that the present invention must rely on the above examples to be implemented. Those skilled in the art should understand that any improvement of the present invention, the equivalent substitution of each raw material of the present invention product, the addition of auxiliary components, and the selection of specific methods, etc., all fall within the protection scope and the disclosure scope of the present invention.

Claims

1. A matte excimer UV-curable anti-graffiti composition, characterized in that, The matte excimer UV-curable anti-graffiti composition comprises the following components in parts by weight: 30 to 60 parts by weight of hyperbranched silicone-modified polyurethane acrylate resin, 30 to 60 parts by weight of active diluent monomer, and 1 to 6 parts by weight of photoinitiator; The functionality of the hyperbranched silicone-modified polyurethane acrylate resin is 4 to 20; The functionality of the active diluent monomer is ≥3; The structural general formula of the hyperbranched silicone-modified polyurethane acrylate resin is selected from any one or a combination of polymers shown by the following structural general formulas; （Ⅰ）； （Ⅱ）； （Ⅲ）； Each R1 is independently selected from any one of substituted or unsubstituted C1-C20 linear or branched alkyl groups, substituted or unsubstituted phenyl groups, and hydroxyl groups; Each R2 and each R3 are independently selected from polyurea urethane residues obtained by reacting amino groups with isocyanate groups or polyamino urethane residues obtained by reacting hydroxyl groups with isocyanate groups; Each R4 is independently selected from polymerization chain segment residues of unsaturated capping monomers and isocyanate groups and has 1 to 5 carbon-carbon double bonds; Each R5 is independently selected from any one of substituted or unsubstituted C1-C20 linear or branched alkylene groups, substituted or unsubstituted C6-C20 arylene groups, substituted or unsubstituted C6-C15 cycloalkylene groups, and -Ar1-L-Ar2-; The chain segment at the end of R4 has 1 to 5 carbon-carbon double bonds.

2. The matte excimer UV-curable anti-graffiti composition according to claim 1, wherein The hyperbranched silicone-modified polyurethane acrylate resin includes one or more of Silok 3826F2, Silok 3826F4, Silok 3826F5, Silok 3826F16, and Silok 3826F20 of Guangzhou Slok Polymer Co., Ltd.; 3. The matte excimer UV-curable anti-graffiti composition according to claim 1, characterized in that, The active diluent monomer is one or more of trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate; 4. The matte excimer UV-curable anti-graffiti composition according to claim 1, characterized in that, The photoinitiator includes one or more of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholin-1-propanone, 1-hydroxy-cyclohexyl-phenylmethanone; 5. The matte excimer UV-curable anti-graffiti composition according to claim 1, characterized in that, By weight, the matte excimer UV-curable anti-graffiti composition further comprises 0 to 2 parts by weight of photosensitizer; 6. The matte excimer UV-curable anti-graffiti composition according to claim 5, characterized in that, The photosensitizer includes one or several of triethanolamine, N,N-dimethylethanolamine, N,N-dimethylaniline, and ethyl 4-(N,N-dimethylamino)benzoate; 7. The matte excimer UV-curable anti-graffiti composition according to claim 1, characterized in that, By weight, the matte excimer UV-curable anti-graffiti composition further comprises 0.3 to 0.5 parts by weight of wetting dispersant and 0 to 0.5 parts by weight of defoamer; 8. The matte excimer UV-curable anti-graffiti composition according to claim 7, characterized in that, The wetting dispersant includes isocyanate group-containing organopolysiloxane; 9. The matte excimer UV-curable anti-graffiti composition according to claim 7, characterized in that, The wetting dispersant includes Silok 3072M2 of Guangzhou Slok Polymer Co., Ltd.; 10. The matte excimer UV-curable anti-graffiti composition according to claim 7, wherein The defoamer includes a mixture of modified silicone and silica.

11. The matte excimer UV-curable anti-graffiti composition according to claim 7, characterized in that, The defoamer includes one or more of Silok 4010, Silok 4013, Silok 4016, and Silok 4019 of Guangzhou Slok Polymer Co., Ltd.

12. Application of the matte excimer UV-curable anti-graffiti composition according to any one of claims 1-11 in excimer UV-curable coatings or excimer UV-curable inks.

13. A matte excimer UV-curable anti-graffiti coating, characterized in that, The matte excimer UV-curable anti-graffiti coating contains the matte excimer UV-curable anti-graffiti composition according to any one of claims 1-11.

14. A method for preparing a matte excimer UV-curable anti-graffiti coating as described in claim 13, characterized in that, It includes the following steps: After coating the matte excimer UV-curable anti-graffiti composition on the surface of the substrate, surface curing is carried out using an ultraviolet excimer lamp. After completing the surface curing, deep curing is then carried out using an ultraviolet lamp to obtain the matte excimer UV-curable anti-graffiti coating.

15. The preparation method according to claim 14, characterized in that, The ultraviolet lamp includes one or more of LED lamps, mercury lamps, xenon lamps, and gallium lamps.

16. The preparation method according to claim 14, characterized in that, The step of deep curing is: First, curing is carried out using an LED lamp, and then curing is carried out using a mercury lamp, xenon lamp, or gallium lamp.

17. An article, characterized in that, It includes a substrate and a coating coated on the substrate, and the coating is the matte excimer UV-curable anti-graffiti coating according to claim 13 or the matte excimer UV-curable anti-graffiti coating prepared according to the preparation method according to any one of claims 14-16.

18. The article according to claim 17, characterized in that, The substrate is any one of a plastic substrate, a wood substrate, a glass substrate, a ceramic plate, and a wall.

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