CN1796478A - Coating material solidified by ultraviolet light and prepartion method - Google Patents
Coating material solidified by ultraviolet light and prepartion method Download PDFInfo
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Abstract
An ultraviolet curing painting, comprising the main resin, the dilution agent and the photo-initiator, and comprising or not comprising the assistant, wherein the said main resin is a mixture of high and low degree of functionality polyurethane acrylate resins, of which the said high degree of functionality polyurethane acrylate resin is a polyurethane acrylate resin with 4-9 double carbon bonds at the end of the molecules, while the said low degree of functionality polyurethane acrylate resin is a polyurethane acrylate resin with 2-3 double carbon bonds at the end of the molecules. Compared with the present processes, the curing coat of the painting has good abrasion resistance and flexibility.
Description
Technical field
The invention relates to a kind of photo-cured coating and preparation method thereof, more specifically say so about a kind of ultraviolet-curing paint and preparation method thereof.
Background technology
Ultraviolet-curing paint (UV coating) is the emerging a kind of coating variety of China recent years, this solids coatings height, dry rapid, the saving energy.
Existing ultraviolet-curing paint contains matrix resin, and thinner and light trigger also contain auxiliary agents such as flow agent, defoamer, lubricant, anti-wear agent sometimes.Wherein, described matrix resin is selected from least a in polyester acrylate, urethane acrylate and the epoxy acrylate.
CN1436825A discloses a kind of ultraviolet-curing paint, this coating is by the aliphatic urethane acrylate of 20-50 weight %, the acrylic modified epoxy resin of 0-20 weight %, the reactive acrylate monomer of 10-50 weight %, the light trigger of 1-5 weight %, the flow agent of 0.3-1 weight %, the defoamer of 0.1-0.5 weight %, 0.5-1.5 the lubricant of weight %, the solvent composition of the anti-wear agent of 0.5-3 weight % and 2-20 weight %.Described solvent is N-BUTYL ACETATE, vinyl acetic monomer, Virahol, ethylene glycol ether acetate or their mixture.
CN1091457C discloses a kind of ultraviolet-curing paint, the component of this coating is: the Epocryl of 5-45% or epoxy methacrylic resin, the aliphatics of 5-45% or alicyclic or aromatic urethane acrylate resin, aliphatics or alicyclic or aromatic urethane methacrylate resin, the butyl acrylate of 10-60% or butyl methacrylate, 3-30% trifunctional group acrylate or trifunctional methacrylic ester, the 1-10% light trigger.
Though above-mentioned coating can be used as the finish paint of woodenware, leather and metal etc. and uses, but, it is applied to plastic fittings, when particularly applying to the portable plastic accessory, because the portable plastic accessory is often moved, easily wear and tear, fold, therefore, require coating to have good wear resistance and snappiness simultaneously, and existing coating wear resistance and flexible over-all properties are relatively poor.
Summary of the invention
The objective of the invention is at existing in prior technology coating lacquer painting wear resistance and the relatively poor defective of flexible over-all properties, a kind of have simultaneously wear resisting property and flexible ultraviolet-curing paint and preparation method thereof preferably are provided.
Existing ultraviolet-curing paint, mostly adopt at least a in aliphatic urethane acrylate, polyester acrylate or the epoxy acrylate as matrix resin, its wear resisting property and snappiness are relatively poor, the present inventor finds, adopt the matrix resin of the mixture of high-functionality polyurethane acrylic resin and low functionality polyurethane acrylate resin as coating, unexpectedly, can improve the wear resistance and the snappiness of lacquer painting greatly.
Coating provided by the invention contains matrix resin, thinner and light trigger, contains or do not contain auxiliary agent, and wherein, described matrix resin is the mixture of high-functionality polyurethane acrylic resin and low functionality polyurethane acrylate resin; Described high-functionality polyurethane acrylic resin is the polyurethane acrylate resin that molecular end contains 4-9 carbon-carbon double bond, and described low functionality polyurethane acrylate resin is the polyurethane acrylate resin that molecular end contains 2-3 carbon-carbon double bond.
The preparation method of coating provided by the invention comprises matrix resin, thinner and light trigger is mixed, described light trigger is dissolved fully, and described matrix resin is dispersed in the described thinner, with the dope filtration that obtains, wherein, described matrix resin is the mixture of high-functionality polyurethane acrylic resin and low functionality polyurethane acrylate resin; Described high-functionality polyurethane acrylic resin is the polyurethane acrylate resin that molecular end contains 4-9 carbon-carbon double bond, and described low functionality polyurethane acrylate resin is the polyurethane acrylate resin that molecular end contains 2-3 carbon-carbon double bond.
Because the present invention adopts the matrix resin of the mixture of high-functionality polyurethane acrylic resin and low functionality polyurethane acrylate resin as coating, thereby improved the wear resistance and the snappiness of lacquer painting greatly, made it reach the coating requirement of high-grade plastic device.For example, the 60 weight % matrix resins that contain provided by the invention, 34 weight % thinners and 6 weight % light triggers, described matrix resin is that the abrasion property that forms of the coating of the mixture of 60 weight %, six functionality aliphatic urethane acrylate resins and 40 weight % three-functionality-degree aliphatic urethane acrylate resins is up to 600, and form identical, be used matrix resin be not that the wear resistance of coating of the mixture of two kinds of matrix resins of the present invention has only 280-350.
Embodiment
According to coating provided by the invention, the content of described matrix resin, thinner, light trigger and auxiliary agent is the content of these component routines in the ultraviolet-curing paint.In general, total amount with coating is a benchmark, the content of described matrix resin is 5-95 weight %, be preferably 12-80 weight %, the content of thinner is 2-90 weight %, is preferably 15-85 weight %, the content of light trigger is 1-10 weight %, be preferably 2-8 weight %, the content of auxiliary agent is 0-15 weight %, is preferably 0-10 weight %.
The matrix resin that uses in the coating provided by the present invention is the mixture of high-functionality polyurethane acrylic resin and low functionality polyurethane acrylate resin.Described polyurethane acrylate resin can be selected from one or more in aliphatic urethane acrylate resin, cycloaliphatic polyurethane acrylate resin and the aromatic urethane acrylate resin, preferred aliphat polyurethane acrylate resin.
Described urethane acrylate can be a kind of xanthochromia type prepolymer, as with aromatic series vulcabond synthetic urethane acrylates such as tolylene diisocyanates, under the preferable case, described urethane acrylate is a kind of non-yellow stain type prepolymer that contains the 2-9 functionality, it can be commercially available, as the urethane acrylate that contains the 2-9 functionality in the product type of BASF (Basfu), lid Si Tafu (Galstaff), Japanese synthetic chemistry Co., Ltd..Also can adopt known method to prepare.For example, vulcabond with no flavescence performance, as isophorone diisocyanate (IPDI), hexamethylene-diisocyanate (HDI) or dicyclohexyl methane diisocyanate (HMDI) synthetic urethane acrylate and polyester glycol reaction, promptly get urethane acrylate with Hydroxyethyl acrylate or Propylene glycol monoacrylate reaction again.It is that second-order transition temperature is between 50-100 ℃ below the 8000cps (25 ℃) that the condition optimization of reaction makes the viscosity of the polyurethane acrylate resin that obtains.The condition of this reaction is conventionally known to one of skill in the art.Can and adopt ammonia ester grafted method according to the hydroxyl groups number, make the end of synthetic urethane acrylate molecule contain the carbon-carbon double bond of different numbers.The number of two keys can be from 2-9, and modal is 2-6.Number according to institute's carbon-carbon double bonds can be divided into urethane acrylate two classes, the urethane acrylate that generally molecular end is contained 2-3 two keys is called low functionality urethane acrylate, and the urethane acrylate that molecular end contains 4-9 two keys is called high-functionality polyurethane acrylic.
The present invention adopts the matrix resin of the mixture of high-functionality polyurethane acrylic resin and low functionality polyurethane acrylate resin as ultraviolet-curing paint.The sense number of degrees of high-functionality polyurethane acrylic are 4-9, and optimum is 5-6.The double key number order of high-functionality polyurethane acrylic resin is more, so its reactive behavior height, the crosslinking curing degree is also high, and it is crosslinked to be easy to form build in solidification process, and has bigger cure shrinkage (cure shrinkage can reach more than 10% sometimes).Thereby the paint film that forms behind ultraviolet light polymerization has very high wear resistance and hardness, but low relatively functionality polyurethane acrylate resin, its sticking power is a bit weaker.And the general viscosity of pure high functional polyurethane resin is bigger, so workability is bad.Low functionality polyurethane acrylate resin is because the double key number order is few, so its reactive behavior is relatively low, and the crosslinking curing degree is low, and cure shrinkage is also less.Thereby the paint film that forms behind ultraviolet light polymerization has higher snappiness, and ground is had higher sticking power.
Based on above-mentioned low functionality polyurethane acrylate resin and high-functionality polyurethane acrylic resin relative merits separately, take all factors into consideration the wear resistance of paint film, hardness, snappiness, sticking power and workability etc. can be used the two, make the coating of formation reach the excellent comprehensive performance.And, can reasonably regulate kind and the ratio of the two according to difference to the various performance requriementss of coating.
According to coating provided by the present invention, though use the mixture of high-functionality polyurethane acrylic resin and low functionality polyurethane acrylate resin can obviously improve the wear resisting property and the snappiness of cured paint film as matrix resin.But, under the preferable case, be benchmark with the gross weight of matrix resin, the content of high-functionality polyurethane acrylic resin is 10-90 weight %, be preferably 30-80 weight %, the content of low functionality polyurethane acrylate resin is 10-90 weight %, is preferably 20-70 weight %.
According to coating provided by the present invention, wherein said thinner is the mixture of organic solvent or organic solvent and acrylate monomer.With the coating gross weight is benchmark, and the content of thinner is 2-90 weight %, is preferably 15-85 weight %.
Wherein said organic solvent is selected from one or more in toluene, ethyl acetate, butylacetate, isobutyl acetate, propyl acetate, ethanol, propyl carbinol, pimelinketone, dimethylbenzene, hexone, acetone, methylethylketone, butyl glycol ether, the propylene glycol butyl ether.
Described acrylate monomer is a ultraviolet-curing paint component commonly used, for conventionally known to one of skill in the art.For example, the single functionality acrylate monomer can be selected from one or more in Hydroxyethyl acrylate (HEA), isobornyl acrylate, isobornyl methacrylate, Isooctyl acrylate monomer, propyl methacrylate, tetrahydrofuran (THF) acrylate, tetrahydrofuran methyl acrylate, glycidyl methacrylate, vinylformic acid caprolactone, the ethoxyquin hydroxyethyl meth acrylate.The difunctionality acrylate monomer can be selected from tri (propylene glycol) diacrylate (TPGDA), 1, in 6 hexanediyl esters (HDDA), 1,6 hexylene glycol dimethyl diacrylate (HDDMA), propylene glycol diacrylate, (2) ethoxyquin bisphenol a dimethacrylate, the polyethyleneglycol diacrylate one or more.Three-functionality-degree diluted acid ester monomer can be selected from one or more in Viscoat 295 (TMPTA), Viscoat 295, trimethylol propane trimethyl triacrylate, (6) ethoxyquin Viscoat 295, (6) third oxidation Viscoat 295s, pentaerythritol triacrylate, (5,5) the high reactivity glycerol propoxylate triacrylate.Four functionality acrylate monomers can be selected from one or more in two-trimethylolpropane tetra-acrylate, tetramethylol methane tetraacrylate, (4) ethoxyquin tetramethylol methane tetraacrylate, five functionality diluted acid ester monomers can be selected from five acrylate and/or tetramethylolmethane five acrylate, and six functionality diluted acid ester monomers can be selected from dipentaerythritol acrylate.According to coating provided by the invention, described acrylate monomer is preferably the acrylate monomer of high functionality, be that functionality is the acrylate monomer of 4-6, the acrylate monomer that adds high functionality can improve the hardness of the coating of coating formation provided by the invention.Gross weight with coating is a benchmark, and the content of described acrylate monomer is 0-30 weight %, is preferably 1-20 weight %.
Light trigger kind described in the coating of the present invention and consumption are conventionally known to one of skill in the art, for example, described light trigger can be selected from IHT-PI185, IHT-PI907, Irgacure651, Irgacure184, Irgacure369, Irgacure754, Irgacure2022, darocur1173, one or more among the darocurMBF.Wherein IHT-PI series is Chinese domestic goods, Irgacure, and darocur series is Switzerland vapour Bagong department product, its trade mark is conventionally known to one of skill in the art.With the coating gross weight is benchmark, and the content of described light trigger is that the content of light trigger is 1-10 weight %, is preferably 2-8 weight %.
Described auxiliary agent refers to one or more in ultraviolet-curing paint flow agent commonly used, defoamer, the dispersion agent.The kind of these auxiliary agents and consumption are conventionally known to one of skill in the art.
The kind of the flow agent described in the present invention and consumption are conventionally known to one of skill in the art, and for example described flow agent can be selected from EFKA3883, EFKA3886, EFKA3600, BYK366, BYK333, among BYK307, the DEGO410 one or more.Wherein EFKA series is Dutch Ai Fuka company product, and BYK series is BYK company product, and DEGO series is German Di Gao company product, more than its trade mark be conventionally known to one of skill in the art.With the coating gross weight is benchmark, and the content of described flow agent is 0-2 weight %, is preferably 0-1.5 weight %.
The kind of the defoamer described in the coating of the present invention and consumption are conventionally known to one of skill in the art, and for example, described defoamer can be selected from EFKA2022, EFKA2527, EFKA2040, BYK352, BYK354, among the BYK357 one or more.With the coating gross weight is benchmark, and the content of described defoamer is 0-2 weight %, is preferably 0-1.5 weight %.
Dispersion agent described in the coating of the present invention refers to any material that can improve described matrix resin dispersion state in solvent, as Kerper-602, and Kerper-605, Kerper630, CFC-500HP, CFC-510, CFC-637, one or more among the CFC-604S.Wherein Kerper series is U.S. Kerper company product, and CFC series is French CFC company product.With the coating gross weight is benchmark, and the content of described dispersion agent is that 0-5 weight % is preferably 0-3 weight %.
Preparation method according to coating provided by the invention, the mixing of described matrix resin, thinner and light trigger can be carried out also simultaneously can proceed step by step, under the preferable case, with light trigger and part mixing diluents, light trigger is fully dissolved, obtain a kind of solution that contains light trigger, matrix resin and part mixing diluents is even, obtain a kind of slurries that contain matrix resin, the solution that will contain light trigger again mixes with the slurries that contain matrix resin, adds remaining diluent at last and mixes.
In order to make described matrix resin homodisperse, during with matrix resin and part mixing diluents, can improve the blended temperature, the blended temperature is conventional mixing temperature, this temperature is generally 30-60 ℃.
If also contain auxiliary agents such as flow agent, defoamer, dispersion agent in the described coating, method provided by the invention also is included in and adds before the remaining diluent, obtaining containing in the slurries of light trigger, matrix resin and described organic solvent, add described flow agent, defoamer, dispersion agent, and the step that mixes.Described flow agent, defoamer, dispersion agent can add simultaneously also and can add step by step, and the order of adding does not have remarkable influence to the performance of coating.
According to method provided by the invention, an embodiment preferred comprises that (1) with light trigger and part mixing diluents, is stirred to abundant dissolving; (2) matrix resin and part mixing diluents is even, (3) mix the product that step (1) and (2) obtain; (4) continue to add or do not add flow agent, defoamer, dispersion agent, and mix; (5) slurries that obtain are filtered in cooling; (6) continue to add remaining diluent, mix.
In method provided by the invention, the consumption of each material should make and obtain in the coating, total amount with coating is a benchmark, the content of described matrix resin is 5-95 weight %, be preferably 12-80 weight %, the content of thinner is 10-90 weight %, is preferably 15-85 weight %, and the content of light trigger is 1-10 weight %, be preferably 2-8 weight %, the content of auxiliary agent is 0-15 weight %, is preferably 0-10 weight %, is benchmark with the amount of described matrix resin, the content of high-functionality polyurethane acrylic resin is 10-90 weight %, be preferably 30-80 weight %, the content of low functionality polyurethane acrylate resin is 10-90 weight %, is preferably 20-70 weight %.
Coating provided by the invention is suitable as the finish paint of the plastic fittings of the finish paint of various material surfaces, particularly portable device, as the finish paint of handset shell surface, portable computer external, makeup shell.Coating thickness is generally the 6-15 micron, 50 ℃ of oven dry 10-15 minute, and, can obtain good solidifying film layer through UV-irradiation 20-25 second.
The following examples will the present invention will be further described.
Embodiment 1
Present embodiment illustrates coating provided by the invention and preparation method thereof.
Prepare coating as follows: (1) is with 6 gram light trigger Irgacure2022 and 10 gram thinner (toluene: ethyl acetate: propyl carbinol=1: 1: 1) mix, be stirred to abundant dissolving; (2) with 36 grams, six functionality aliphatic urethane acrylate resins (Japanese synthetic chemistry Co., Ltd. product, model UV-7605B) and 24 three-functionality-degree aliphatic urethane acrylate resin (UCB. S.A.'s products, model Ebecryl 264) restrain thinner (toluene: ethyl acetate: propyl carbinol=1: 1: 1) mix with 15 at 40 ℃, stir, (3) mix the product that step (1) and (2) obtain; (4) cooling is filtered the slurries that obtain, to remove residue; (5) continue to add 9 gram thinner (toluene: ethyl acetate: propyl carbinol=1: 1: 1), stir, obtain coating T1.Table 1 has provided the composition of T1.
Comparative Examples 1-4
Following Comparative Examples explanation reference coating and preparation method thereof.
Method according to embodiment 1 prepares coating, different is, in Comparative Examples 1, restrain aliphatic urethane acrylate resin (Sartomer products with 30, CN965), 15 gram Epocryl (galstaff products, syncryl104) and 15 gram polyester acrylate resin (Sartomer products, CNUVP225) replace 36 grams, six functionality aliphatic urethane acrylate resins (Japanese synthetic chemistry Co., Ltd. product, model UV-7605B) and 24 the gram three-functionality-degree aliphatic urethane acrylate resins (UCB. S.A.'s product, model Ebecryl 264); In Comparative Examples 2, restrain aliphatic urethane acrylate resin (Sartomer products with 30, CN965) and 30 gram Epocryl (galstaff products, syncryl104) replace 36 grams, six functionality aliphatic urethane acrylate resins (Japanese synthetic chemistry Co., Ltd. product, model UV-7605B) and 24 the gram three-functionality-degree aliphatic urethane acrylate resins (UCB. S.A.'s product, model Ebecryl 264); In Comparative Examples 3, restrain aliphatic urethane acrylate resin (Sartomer products with 30, CN965) and 30 gram polyester acrylate resin (Sartomer products, CNUVP225) replace 36 grams, six functionality aliphatic urethane acrylate resins (Japanese synthetic chemistry Co., Ltd. product, model UV-7605B) and 24 the gram three-functionality-degree aliphatic urethane acrylate resins (UCB. S.A.'s product, model Ebecryl 264); In Comparative Examples 4 with 60 grams, six functionality aliphatic urethane acrylate resins (Japanese synthetic chemistry Co., Ltd. product, model UV-7605B) replaces 36 grams, six functionality aliphatic urethane acrylate resins (Japanese synthetic chemistry Co., Ltd. product, model UV-7605B) and 24 the gram three-functionality-degree aliphatic urethane acrylate resins (UCB. S.A.'s product, model Ebecryl 264).Obtain reference coating TC1-TC4.Table 1 has provided the composition of TC1-TC4.
Embodiment 2
Present embodiment illustrates coating provided by the invention and preparation method thereof.
Prepare coating as follows: (1) is with 3 gram light trigger Irgacurel84 and 7 gram thinner (butylacetates: ethanol: pimelinketone: butyl glycol ether=1: 1: 1: 1) mix, be stirred to abundant dissolving; (2) with 12 grams, six functionality aliphatic urethane acrylate resins (Japanese synthetic chemistry Co., Ltd. product, model UV-7605B) and 18 the gram two functionality aliphatic urethane acrylate resin (Galstaff company products, model 305) with 30 gram thinner (butylacetate: ethanol: pimelinketone: butyl glycol ether=1: 1: 1: 1) mix at 40 ℃, stir, (3) mix the product that step (1) and (2) obtain; (4) cooling is filtered the slurries that obtain, to remove residue; (5) continue to add 30 gram thinner (butylacetates: ethanol: pimelinketone: butyl glycol ether=1: 1: 1: 1), stir, obtain coating T2.Table 1 has provided the composition of T2.
Table 1
| The embodiment numbering | Embodiment 1 | Comparative Examples 1 | Comparative Examples 2 | Comparative Examples 3 | Comparative Examples 4 | Embodiment 2 |
| Finish code | T1 | TC1 | TC2 | TC3 | TC4 | T2 |
| Matrix resin content, weight % | 60 | 60 | 60 | 60 | 60 | 30 |
| Photoinitiator levels, weight % | 6 | 6 | 6 | 6 | 6 | 3 |
| Amount of diluent, weight % | 34 | 34 | 34 | 34 | 34 | 67 |
Embodiment 3
Present embodiment illustrates coating provided by the invention and preparation method thereof.
Prepare coating as follows: (1) is with 3 gram light trigger Irgacure2959 and 10 gram thinner (isobutyl acetates: propyl carbinol: propylene glycol butyl ether=1: 2: 1) mix, be stirred to abundant dissolving; (2) with 20 grams, six functionality aliphatic urethane acrylate resins (Japanese synthetic chemistry Co., Ltd. product, model UV-7605B), 20 grams, two functionality aliphatic urethane acrylate resin (Galstaff company products, model 305), 6 gram tetramethylol methane tetraacrylates and 6 gram dipentaerythritol acrylates and 25 gram thinner (isobutyl acetates: propyl carbinol: propylene glycol butyl ether=1: 2: 1) mix at 40 ℃, stir, (3) mix the product that step (1) and (2) obtain; (4) cooling is filtered the slurries that obtain, to remove residue; (5) continue to add 10 gram thinner (isobutyl acetates: propyl carbinol: propylene glycol butyl ether=1: 2: 1), stir, obtain coating T3.Table 2 has provided the composition of T3.
Embodiment 4
Present embodiment illustrates coating provided by the invention and preparation method thereof.
Prepare coating as follows: (1) is with 8 gram light trigger Irgacure2959 and 10 gram thinner (isobutyl acetates: propyl carbinol: propylene glycol butyl ether=1: 2: 1) mix, be stirred to abundant dissolving; (2) with 20 grams, six functionality aliphatic urethane acrylate resins (Japanese synthetic chemistry Co., Ltd. product, model UV-7605B), 30 gram trifunctional aliphatic urethane acrylate resin (UCB. S.A.'s products, model Ebecryl 264), 5 gram tetramethylol methane tetraacrylates and 10 gram dipentaerythritol acrylates restrain thinner (isobutyl acetates: propyl carbinol: propylene glycol butyl ether=1: 2: 1) mix at 40 ℃ with 50, stir, (3) mix the product that step (1) and (2) obtain; (4) in the product that step (3) obtains, add 2.0 gram flow agent EFKA3883,0.8 gram defoamer BYK052,2.0 gram dispersion agent Kerper-605 stir; (5) cooling is filtered the slurries that obtain, to remove residue; (6) continue to add 20 gram thinner (isobutyl acetates: propyl carbinol: propylene glycol butyl ether=1: 2: 1), stir, obtain coating T4.Table 2 has provided the composition of T4.
Table 2
| The embodiment numbering | 3 | 4 |
| Finish code | T3 | T4 |
| Matrix resin content, weight % | 40 | 31.7 |
| Photoinitiator levels, weight % | 3 | 5.1 |
| Amount of diluent, weight % | 45 | 50.7 |
| High functional group acrylate monomer, weight % | 12 | 9.5 |
| Dispersant, weight % | - | 1.3 |
| Flow agent content, weight % | - | 1.3 |
| Antifoam content, weight % | - | 0.5 |
Embodiment 5-12
Coating wear resistance, hardness, sticking power, folding resistance (snappiness) and glossiness that the following examples explanation embodiment of the invention 1-4 and Comparative Examples 1-4 are provided.
Coating T1-T4 and TC1-TC4 that embodiment 1-4 and Comparative Examples 1-4 are obtained are sprayed on the plastic casing, and 50 ℃ of oven dry 15 minutes, and through UV-irradiation 25 seconds obtain thickness and be 12 microns solidifying film layer.Wear resistance, hardness, sticking power, folding resistance (snappiness) and the glossiness of test solidifying film layer, the result is as shown in table 3.
Wear resistance is measured: the 7-IBB type RCA abrasion instrument that uses U.S. Nuo Man Instrument and Equipment Company to produce, and under the effect of 175 gram forces, the paint film after the mill spraying, during the show-through material of paint film, the number of times that rubber wheel rotates.
Sticking power is measured: draw 100 1 millimeter * 1 millimeter square lattice at sprayed surface with drawing the lattice device, the model of producing with Minnesota Mining and Manufacturing Company is 600 smooth being bonded on the grid of scotch tape, do not stay a space, vertically uncover with utmost dispatch then, observe cut edge and have or not depainting.Is 5B as the depainting amount between 0-5%, is 4B between 5-10%, is 3B between 10-20%, is 2B between 20-30%, is B between 30-50%, is being 0B more than 50%.
Measurement of hardness: carry out according to chapter 4 regulation among the GB/6739T.
Folding resistance test: the paint film model for preparing is carried out 90 ° fold, observe coating surface and have or not big area explosion phenomenon, with behind its recovery plane, observe paint and have or not peeling phenomenon then.Think then that as the no peeling phenomenon of paint snappiness is good in embodiments of the present invention, paint has a little peeling phenomenon to think that then snappiness is general, and paint has serious peeling phenomenon to think that then snappiness is poor.
Glossiness is measured: adopt miniature vancometer (BYK production) to test under 60 ° of angles and obtain the glossiness data.In embodiments of the present invention as glossiness greater than then thinking the glossiness height more than 95, think that with next glossiness is general 95.
Table 3
| Finish code | The mensuration project | |||||
| Wear resistance (inferior) | Hardness | Sticking power | Folding resistance | Form the painted surface situation | ||
| Embodiment 1 | T1 | 600 | 3H | 5B | No peeling phenomenon | Outstanding, surfacing, glossiness height |
| Embodiment 2 | T2 | 550 | 2H | 5B | No peeling phenomenon | Outstanding, surfacing, glossiness height |
| Embodiment 3 | T3 | 450 | 3H | 5B | No peeling phenomenon | Outstanding, surfacing, glossiness height |
| Embodiment 4 | T4 | 560 | 4H | 5B | No peeling phenomenon | Outstanding, surfacing, glossiness height |
| Comparative Examples 1 | TC1 | 280 | 1H | 5B | No peeling phenomenon | Outstanding, surfacing, glossiness is general |
| Comparative Examples 2 | TC2 | 300 | 2H | 5B | No peeling phenomenon | Outstanding, surfacing, glossiness height |
| Comparative Examples 3 | TC3 | 350 | 2H | 5B | A little peeling phenomenon is arranged | Outstanding, surfacing, glossiness is general |
| Comparative Examples 4 | TC4 | 610 | 3H | 2B | Serious peeling phenomenon is arranged | Outstanding, surfacing, glossiness height |
From the result of table 3 as can be seen, abrasion property and snappiness that coating provided by the present invention forms all reach very high level, have kept good sticking power and painted surface situation simultaneously.The non-constant of abrasion property energy that the coating that Comparative Examples 1-3 obtains forms, though and the abrasion property energy that the coating that Comparative Examples 4 obtains forms is better, be on close level with the coating that coating provided by the invention forms, still, its snappiness and sticking power are very poor.In embodiment 4, owing to added the acrylate monomer of high functionality, the coating that the coating that obtains forms has excellent abrasive resistance and flexible while, and hardness has also obtained bigger raising.The above results shows that the coating that coating provided by the present invention forms has excellent abrasive and flexible over-all properties.
Claims (16)
1, a kind of ultraviolet-curing paint, this coating contains matrix resin, thinner and light trigger, contain or do not contain auxiliary agent, it is characterized in that described matrix resin is the mixture of high-functionality polyurethane acrylic resin and low functionality polyurethane acrylate resin; Described high-functionality polyurethane acrylic resin is the polyurethane acrylate resin that molecular end contains 4-9 carbon-carbon double bond, and described low functionality polyurethane acrylate resin is the polyurethane acrylate resin that molecular end contains 2-3 carbon-carbon double bond.
2, coating according to claim 1 is characterized in that, is benchmark with the gross weight of coating, the content of described matrix resin is 5-95 weight %, the content of thinner is 2-90 weight %, and the content of light trigger is 1-10 weight %, and the content of auxiliary agent is 0-15 weight %.
3, coating according to claim 2 is characterized in that, is benchmark with the gross weight of coating, the content of described matrix resin is 12-80 weight %, the content of thinner is 15-85 weight %, and the content of light trigger is 2-8 weight %, and the content of auxiliary agent is 0-10 weight %.
4, coating according to claim 1 is characterized in that, described polyurethane acrylate resin is selected from one or more in aliphatic urethane acrylate, cycloaliphatic polyurethane acrylate resin and the aromatic urethane acrylate resin.
5, coating according to claim 1 is characterized in that, the molecular end of described high-functionality polyurethane acrylic resin contains 5-6 carbon-carbon double bond.
6, coating according to claim 1, it is characterized in that, gross weight with matrix resin is a benchmark, and the content of described high-functionality polyurethane acrylic resin is 10-90 weight %, and the content of described low functionality polyurethane acrylate resin is 10-90 weight %.
7, coating according to claim 6, it is characterized in that, gross weight with matrix resin is a benchmark, and the content of described high-functionality polyurethane acrylic resin is 30-80 weight %, and the content of described low functionality polyurethane acrylate resin is 20-70 weight %.
8, coating according to claim 1 is characterized in that described thinner is the mixture of organic solvent or organic solvent and acrylate monomer.
9, coating according to claim 8, wherein said organic solvent are selected from one or more in toluene, ethyl acetate, butylacetate, isobutyl acetate, propyl acetate, ethanol, propyl carbinol, pimelinketone, dimethylbenzene, hexone, acetone, methylethylketone, butyl glycol ether, the propylene glycol butyl ether.
10, coating according to claim 8 is characterized in that, is benchmark with the coating gross weight, and the content of described acrylate monomer is 0-30 weight %.
11, coating according to claim 10 is characterized in that, is benchmark with the coating gross weight, and the content of described acrylate monomer is 1-20 weight %.
According to claim 10 or 11 described coating, it is characterized in that 12, described acrylate monomer is the acrylate monomer of high functionality.
13, the preparation method of the described coating of claim 1, this method comprises mixes matrix resin, thinner and light trigger, described light trigger is dissolved fully, and described matrix resin is dispersed in the described thinner, with the dope filtration that obtains, it is characterized in that described matrix resin is the mixture of high-functionality polyurethane acrylic resin and low functionality polyurethane acrylate resin; Described high-functionality polyurethane acrylic resin is the polyurethane acrylate resin that molecular end contains 4-9 carbon-carbon double bond, and described low functionality polyurethane acrylate resin is the polyurethane acrylate resin that molecular end contains 2-3 carbon-carbon double bond.
14, method according to claim 13 is characterized in that, described matrix resin, thinner and light trigger blended step be, with light trigger and part mixing diluents, light trigger is fully dissolved, and obtains a kind of solution that contains light trigger; Matrix resin and part mixing diluents is even, obtain a kind of slurries that contain matrix resin; The solution that will contain light trigger mixes with the slurries that contain matrix resin, adds remaining diluent at last and mixes.
15, method according to claim 14, it is characterized in that this method also is included in and adds before the remaining diluent, in the slurries that contain light trigger, matrix resin and described organic solvent that obtain, add flow agent, defoamer and/or dispersion agent, and the step that mixes.
16. method according to claim 13 is characterized in that, this method comprises that (1) with matrix resin and part mixing diluents, is stirred to abundant dissolving; (2) light trigger and part mixing diluents is even; (3) product that step (1) and (2) are obtained mixes; (4) continue to add or do not add flow agent, defoamer and/or dispersion agent, and mix; (5) slurries that obtain are filtered in cooling; (6) continue to add remaining diluent, mix.
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| CNB200410101453XA CN100448939C (en) | 2004-12-20 | 2004-12-20 | Coating material solidified by ultraviolet light and prepartion method |
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| CNB200410101453XA CN100448939C (en) | 2004-12-20 | 2004-12-20 | Coating material solidified by ultraviolet light and prepartion method |
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| CNB200410101453XA Expired - Fee Related CN100448939C (en) | 2004-12-20 | 2004-12-20 | Coating material solidified by ultraviolet light and prepartion method |
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