CN102220084A - Photocureable coating and curing method thereof - Google Patents
Photocureable coating and curing method thereof Download PDFInfo
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- CN102220084A CN102220084A CN2010101552913A CN201010155291A CN102220084A CN 102220084 A CN102220084 A CN 102220084A CN 2010101552913 A CN2010101552913 A CN 2010101552913A CN 201010155291 A CN201010155291 A CN 201010155291A CN 102220084 A CN102220084 A CN 102220084A
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Abstract
The invention provides a photocureable coating and a curing method thereof. The photocureable coating comprises main resin, a main photoinitiator, an active monomer, a coloring agent and organic solvent, wherein the main resin contains urethane acrylate resin and/or polyester acrylate, the activation wave length of the main photoinitiator ranges from 380 to 430nm, and the coloring agent is an acetic acid butyrate cellulose colored sheet. By adopting the photocureable coating, monolayer of the colored coating is realized, the process steps can be simplified, and the production efficiency is improved; the coating has good performance in various aspects, good apparent performance, and uniform color without dazzling.
Description
Technical field
The present invention relates to a kind of photo-cured coating and curing thereof, especially a kind of photo-cured coating and curing thereof that contains pigment.
Background technology
Present electronic product casings such as mobile phone, digital camera, notebook computer, after machine-shaping, need be at its external coating coating, decorate and protect.Usually require to have good surface properties behind the coating curing of application, especially glossiness.
Traditional decorative coating is two-layer, i.e. priming paint and finish paint.Priming paint provides good sticking power and toning effect, and finish paint provides excellent surface property, as glossiness.Above-mentioned coating is being coated with when installing on the product casing, the coating process that adopts is that coating prime lacquer is painted usually, and the finish paint of the different bright mute degree of application is protected again.Need two or more processing procedures like this, it is low to exist efficient, shortcomings such as energy consumption height, therefore, develop a kind of high performance single coating coating, keep good performance in painted having had to decorate, replacing the overbrushing layer and decorate, is the most effective enhancing productivity, the approach that reduces cost.
In order to satisfy the requirement of single coating, what adopt usually in the prior art is individual layer urethane colored paint, by adding pigment in polyurethane coating, thereby obtains the good individual layer colored paint of physicals.But, in polyurethane coating, for make pigment can be in coating homodisperse, thereby guarantee that the problem of growing dim does not appear in coating, the hydroxyl value of polyurethane coating can not be high; At this moment, lower hydroxyl value can influence the curing speed of polyurethane coating again.For example, existing Workpiece painting polyurethane coating needed behind the following part to place several days or 80 ℃ of pressure bakings can reach the coating performance requirement in 4 hours, and product line running efficiency is low.
Summary of the invention
Low in order to solve in the prior art decorative coveringn production efficiency, the problem that curing speed is slow the invention provides a kind of photo-cured coating, and it is fast to form single-layer coating after fixing speed by this photo-cured coating at substrate surface, and the color quality height.
Photo-cured coating disclosed by the invention comprises matrix resin, key light initiator, reactive monomer, tinting material and organic solvent, described matrix resin contains polyurethane acrylate resin and/or polyester acrylate, and the activation wavelength of described key light initiator is 380-430nm; Described tinting material is the cellulose acetate butyrate color chips.
Simultaneously, the invention also discloses the curing of above-mentioned photo-cured coating, comprise photo-cured coating is coated on the base material, be cured; Described condition of cure is: wavelength 280-450nm, solidify energy 800-1200mj/cm
2, be 20-30s set time; Wherein, described photo-cured coating is above-mentioned photo-cured coating.
Adopt photo-cured coating disclosed by the invention to be sprayed at substrate surface, after solidifying, can form the individual layer colored coating of excellent performance, simplified technology, improved production efficiency.
The present inventor's discovery in a large amount of experiments, when adopting photo-cured coating to prepare colored coating, owing to blocking and sorption of pigment, the paint solidification difficulty, and curing speed is slow.Especially the coating depths is difficult to effectively be solidified.In addition, the pigment in the coating also is difficult to disperse, and has influenced the physicals of coating to a certain extent.The contriver adopts coating disclosed by the invention, by the acting in conjunction of light initiation system and tinting material, coating can effectively be solidified, and tinting material can be in coating homodisperse, improved physicals greatly.
Embodiment
In order to make technical problem solved by the invention, technical scheme and beneficial effect clearer,, the present invention is further elaborated below in conjunction with drawings and Examples.Should be appreciated that specific embodiment described herein only in order to explanation the present invention, and be not used in qualification the present invention.
Photo-cured coating disclosed by the invention comprises matrix resin, key light initiator, reactive monomer, tinting material and organic solvent, described matrix resin contains polyurethane acrylate resin and/or polyester acrylate, and the activation wavelength of described key light initiator is 380-430nm; Described tinting material is cellulose acetate butyrate color chips (a CAB color chips).
According to the present invention, the median size of described cellulose acetate butyrate color chips is 50-100nm, is preferably 60-90nm.Above-mentioned cellulose acetate butyrate color chips all can be commercially available, as the CAB color chips of sun Chemical Corporation's production.
When the contriver found that median size when described cellulose acetate butyrate color chips is in above-mentioned scope, by the acting in conjunction of key light initiator and cellulose acetate butyrate color chips, coating can obtain more effective curing, and especially coating depths solidification effect is good.Thereby improve the physicals of coating.
For key light initiator disclosed by the invention, can adopt various activation wavelength is that the light trigger of 380-430nm, especially activation wavelength are the light trigger of 390-400nm.Under the preferable case, described key light initiator can be the phosphorus oxide photoinitiator, for example, can adopt in amyl group phosphorus oxide, phenyl phosphorus oxide, the diphenyl phosphate oxidation one or more.Wherein, described amyl group phosphorus oxide can be two (2,6-dimethoxy benzoyl)-(2,4,4-trimethylammonium-penta-1-yl) phosphorus oxide, two (2,4,6-trimethoxy benzoyl)-(2,4-two pentyloxy phenyl) phosphorus oxide; Described phenyl phosphorus oxide can be 2,4,6-trimethylbenzoyl diphenyl phosphate oxidation, two (2,4,6-Three methyl Benzene formyl) phenyl phosphorus oxide; Described diphenyl phosphate oxidation can be (2,4,6-trimethylbenzoyl phenylbenzene) phosphorus oxide.Above-mentioned key light initiator all can be commercially available, and as the IRGACURE 2100 that Ciba company produces, IRGACURE 819, and IRGACURE 2022.
In photo-cured coating disclosed by the invention, various components contents can change in a big way, under the preferable case, with described matrix resin content is benchmark, described reactive monomer content is 150-200wt%, described key light initiator content is 25-50wt%, and described colorant content is 2-8wt%, and described organic solvent content is 150-250wt%; More preferably reactive monomer content is 160-200wt%, and described key light initiator content is 30-45wt%, and described colorant content is 2-6wt%, and described organic solvent content is 200-220wt%.
Usually, in existing photo-cured coating, add a spot of pigment after, coating also can be realized solidifying, but because the restriction of pigment content, the color effect of coating is also bad.As can be seen, in the coating disclosed by the invention, colorant content is bigger, and at this moment, this photo-cured coating still can effectively solidify.And can make the color of coating more bright-coloured by the tinting material that adds the content instruction, can improve the color vision effect of coating greatly.
According to photo-cured coating disclosed by the invention, described matrix resin contains polyurethane acrylate resin and/or polyester acrylate.Under the preferable case, described matrix resin is polyurethane acrylate resin and polyester acrylate
Wherein, 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.Its 60 ℃ of following viscosity are 500-4500cps, and functionality is 4-6.Being preferably 60 ℃ of following viscosity is 500-2200cps, and functionality is 5-6.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 5-6 functionality, it can be commercially available, as the urethane acrylate that contains the 5-6 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 500-2200cps (60 ℃) 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 2-6, and modal is 4-6.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 4-6 two keys is called high-functionality polyurethane acrylic.
Equally, described polyester acrylate can adopt this area polyester acrylate commonly used, is 1300-4500 60 ℃ of following viscosity, and functionality is 2-4.Being preferably 60 ℃ of following viscosity is 1500-4000cps, and functionality is 2-3.The polyester acrylate that satisfies above-mentioned condition can be commercially available, Sartomer for example, and BASF contains the polyester acrylic resin of 2-4 functional group in the product type of Baeyer.
As preferred embodiment a kind of, described matrix resin is polyurethane acrylate resin and polyester acrylate, and wherein, the content of polyurethane acrylate resin and polyester acrylate is than being 1.5-1: 1, and 1.2-1 more preferably: 1.In photo-cured coating disclosed by the invention,, can improve the stability and the physicals of coating greatly by polyurethane acrylate resin and polyester acrylate are used jointly.
In addition, among the present invention, described reactive 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, tripropylene 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), 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.Under the preferable case, according to photo-cured coating provided by the invention, described reactive monomer is preferably one or more in hexanediyl ester, tripropylene glycol diacrylate, pentaerythritol triacrylate, Viscoat 295, the dipentaerythritol acrylate.The reactive monomer that adopts in the photo-cured coating disclosed by the invention can be commercially available, as SR238, SR306, SR351, the SR444 etc. of Sartomer company production.
The organic solvent that adopts in the above-mentioned photo-cured coating is various organic solvents commonly used in the prior art, for example, this organic solvent can be 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 and the propylene glycol butyl ether.Under the preferable case, can adopt mixed solvent, be acetone as each components by weight: Virahol: the mixed solvent of ethylene glycol uncle butyl ether=6: 3: 1.
In addition, also contain the fill-in light initiator in the described photo-cured coating, the activation wavelength of described fill-in light initiator is 300-369nm, is preferably 330-365nm.Described fill-in light initiator is selected from one or more in alpha hydroxy ketone light trigger or the benzophenone-tertiary amines light trigger; With described matrix resin content is benchmark, and described fill-in light initiator content is 10-20wt%, is preferably 15-20wt%.
Concrete, above-mentioned alpha hydroxy ketone light trigger can be 2-hydroxy-2-methyl-1-phenyl-acetone, 1-hydroxy cyclohexyl phenylketone, 2-phenmethyl-2-dimethylamino-1-(4-morphine base phenyl)-butanone, 2-methyl isophthalic acid (4-(methylthio group) phenyl)-2-morphine-1-acetone.Above-mentioned benzophenone-tertiary amines light trigger can be benzophenone, 4,4 '-two phenoxy group benzophenone.
The present inventor finds by a large amount of experiments, when also containing above-mentioned fill-in light initiator in the photo-cured coating disclosed by the invention, the acting in conjunction of the initiator system of forming by fill-in light initiator and key light initiator, in above-mentioned photo-cured coating, can better realize solidifying, and very favourable to the homogeneity of the physicals, stability and the color that improve coating.
In order to improve the over-all properties of photo-cured coating disclosed by the invention, under the preferable case, also contain in flow agent, dispersion agent, defoamer, the anti-settling agent one or more in the described photo-cured coating; And, with described matrix resin content is benchmark, described flow agent content is 0-2wt%, be preferably 0.5-1.5wt%, described dispersant is 0-10wt%, is preferably 4-8wt%, described antifoam content is 0-1.6wt%, be preferably 0.6-1.4wt%, described anti-settling agent content is 0-2wt%, is preferably 0.8-1.6wt%.
According to the present invention, above-mentioned flow agent can variously can improve the flow leveling that is coated with rete behind the paint solidification for well known to a person skilled in the art, increase the material of the smoothness and the feel that are coated with rete, for example, can be selected among EFKA3883, EFKA3886, EFKA3600, BYK366, BYK333, BYK307, DEGO410, DEGO435, DEGO432, the TEGO Flow300 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, and TEGO is the product of German TEGO company.
According to photo-cured coating provided by the invention, the kind of described defoamer is as well known to those skilled in the art, for example, described defoamer can be selected EFKA2022, EFKA2527 and the EFKA2040 of the Dutch Ai Fuka company that is purchased, the BYK352 of BYK company, BYK354 and BYK357 for use.
Dispersion agent described in the photo-cured coating disclosed by the invention refers to any material that can improve described matrix resin dispersion state in solvent, as Kerper-602, and Kerper-605, Kerper-630, 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.
The effect of described anti-settling agent in coating composition is to form powerful network structure, makes system have excellent thixotropic property, can effectively prevent component sedimentation and knot lump in the coating.Described anti-settling agent can be selected various anti-settling agent of the prior art for use, for example can be in the anti-heavy wax slurry of organically-modified boron-moisten soil, polymeric amide, the aerosil one or more, the 201P, 229 that the Taiwan moral is modest, the DS6500/6800-20X of U.S. TAVY, DS5000-10X, the anti-settling agents that 6900-20X, 4200-10 that the Japan nanmu originally changes into or Degussa company and ROCKWOOD company produce etc., the above trade mark is conventionally known to one of skill in the art.
It doesn't matter each other for the content of above flow agent, dispersion agent, defoamer, anti-settling agent, and only need making separately, content is getting final product in the scope separately.
Above-mentioned photo-cured coating can be prepared by method of the prior art, as the various components of photo-cured coating are mixed.The mixing of described matrix resin, reactive monomer, organic solvent and key light initiator, tinting material can be carried out also simultaneously can proceed step by step, under the preferable case, tinting material is mixed with part reactive monomer, part organic solvent, obtain a kind of solution of tinting material, matrix resin and part reactive monomer, part organic solvent are mixed, obtain a kind of slurries that contain matrix resin, the slurries that will contain the solution of tinting material again and contain matrix resin mix, and add the key light initiator at last and remaining organic solvent mixes.When containing the fill-in light initiator, fill-in light initiator and key light initiator together add.
If also contain in flow agent, dispersion agent, defoamer, the anti-settling agent one or more in the described coating, before method provided by the invention also is included in and adds remaining organic solvent, containing the key light initiator, contain or do not contain in the slurries of fill-in light initiator, matrix resin, reactive monomer, organic solvent, tinting material, add described flow agent, dispersion agent, defoamer, anti-settling agent, and the step that mixes.Described flow agent, dispersion agent, defoamer, anti-settling 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.
As the application to photo-cured coating disclosed by the invention, the present invention also discloses the curing of above-mentioned photo-cured coating, comprises photo-cured coating is coated on the base material, is cured; Described condition of cure is: wavelength 280-450nm, solidify energy 800-1200mj/cm
2, be 20-30s set time; Wherein, described photo-cured coating is above-mentioned photo-cured coating.Under the preferable case, described condition of cure is: wavelength 300-430nm, solidify energy 1000-1200mj/cm
2, be 25-30s set time.
Under the preferable case, when being cured, the light that light source sends has the multi-wavelength, can cover the 280-450nm wavelength region.
According to the present invention, when being coated in photo-cured coating on the base material, the coat-thickness of formation is 10-30um.Be preferably 15-25um.
Usually, for the coating that contains pigment, its thickness is thin more, and it is easy more to solidify, and thickness is thick more, and it is difficult more to solidify, and the difficult solidified problem of deep layer is obvious more.The contriver finds, adopts photo-cured coating disclosed by the invention, even coat-thickness is bigger, also can effectively solidify deep layer.
In the aforesaid method, substrate surface apply the method for this photo-cured coating can be for this area in blade coating, spraying, roller coat or brushing commonly used, this method as well known to those skilled in the art repeats no more once more.
Described curing can adopt existing various uv equipment to carry out, as comprising visible light or/and the light source of ultraviolet wavelength light wave for sending, and such as medium pressure mercury lamp, low pressure mercury lamp, high voltage mercury lamp, electrodeless lamp, xenon lamp, metal halide lamp etc.Among the present invention, described curing can be carried out in the F300 ultra-violet curing lamp system that FUSION company produces.
Photo-cured coating disclosed by the invention can be applicable to various substrate surfaces, as plastics, metal etc.
The present invention is further illustrated below by embodiment.
Embodiment 1
Present embodiment is used to illustrate photo-cured coating disclosed by the invention and curing thereof.
With 2.4 weight part cellulose acetate butyrate color chips (CAB color chips, sun Chemical Corporation produces, median size is 95nm) with 50 weight part butylacetates, 55 weight part reactive monomer (Viscoat 295s, the SR351 that Sartomer company produces) mixes, stir, obtain containing the solution of tinting material.
With 100 weight part polyurethane acrylate resin (aliphatic urethane acrylates, the 6145-100 resin that Changxing chemical company produces, 60 ℃ of following viscosity are 4000cps, functionality is 6), 100 weight part reactive monomer (Viscoat 295s, the SR351 that Sartomer company produces) mixes with 70 weight part butylacetates, obtain containing the solution of matrix resin.
Above two kinds of solution are mixed; and add 27 weight part key light initiators (two (2; 6-dimethoxy benzoyl)-(2; 4; 4-trimethylammonium-penta-1-yl) phosphorus oxide, the IRGACURE 819 that Ciba company produces, activation wavelength is 380-420nm), 40 weight part butylacetates; stir, obtain photo-cured coating S10.
Spraying photo-cured coating S10 forms the thick coating of 28um on plastic basis material.
The base material of the surface being had coating places the F300 ultra-violet curing lamp system of FUSION company production to be cured, and condition of cure is wavelength 290-430nm, solidifies energy 900mj/cm
2, be 30s set time.
Obtain sample S1.
Embodiment 2
Present embodiment is used to illustrate photo-cured coating disclosed by the invention and curing thereof.
With 7 weight part cellulose acetate butyrate color chips (CAB color chips, sun Chemical Corporation produces, median size is 55nm) with 80 weight part butyl glycol ethers, 80 weight part reactive monomer (pentaerythritol triacrylates, the SR444 that Sartomer company produces) mixes, stir, obtain containing the solution of tinting material.
(BASF AG produces with 100 weight part polyester acrylate resins, 60 ℃ of following viscosity are 4000cps, functionality is 3.6), 110 weight part reactive monomer (pentaerythritol triacrylates, the SR444 that Sartomer company produces) mixes with 100 weight part butyl glycol ethers, obtain containing the solution of matrix resin.
Above two kinds of solution are mixed, and add 48 weight part key light initiators (two (2,4,6-Three methyl Benzene formyl) phenyl phosphorus oxide, the DAROCUR 4265 that Ciba company produces, activation wavelength is 390-410nm), 1.2 weight part anti-settling agents (6900-20X that the Japanese nanmu company that originally changes into produces), 6 weight part dispersion agents (Kerper-602 that Kerper company produces), 60 weight part butyl glycol ethers, stir, obtain photo-cured coating S20.
Spraying photo-cured coating S20 forms the thick coating of 12um on plastic basis material.
The base material of the surface being had coating places the F300 ultra-violet curing lamp system of FUSION company production to be cured, and condition of cure is wavelength 300-440nm, solidifies energy 1000mj/cm
2, be 22s set time.
Obtain sample S2.
Embodiment 3
Present embodiment is used to illustrate photo-cured coating disclosed by the invention and curing thereof.
With 5 weight part cellulose acetate butyrate color chips (CAB color chips, sun Chemical Corporation produces, median size is 80nm) with ethylene glycol uncle butyl ether=6: 3: 1), 70 weight part reactive monomers (1 50 weight part organic solvents (acetone: Virahol:, 6 hexanediyl esters, the SR238 that Sartomer company produces) mixes, stir, obtain containing the solution of tinting material.
With 55 weight part polyurethane acrylate resins (the 6141H-80 resin that Changxing chemical company produces, 60 ℃ of following viscosity are 1000cps, functionality is 5), (BASF AG produces 45 weight part polyester acrylate resins, 60 ℃ of following viscosity are 3000cps, functionality is 3), 90 weight part reactive monomers (1,6 hexanediyl esters, the SR238 that Sartomer company produces) with 90 weight part organic solvents (acetone: Virahol: ethylene glycol uncle butyl ether=6: 3: 1) mix, obtain containing the solution of matrix resin.
Above two kinds of solution are mixed; and add 32 weight part key light initiators ((2; 4; 6-trimethylbenzoyl phenylbenzene) phosphorus oxide; the DARUCUR 4265 that Ciba company produces; activation wavelength is 390-410nm), 12 weight part fill-in light initiator (1-hydroxy cyclohexyl phenylketones; the DAROCUR BP that Ciba company produces; activation wavelength is 300-360nm), 40 weight part organic solvents (acetone: Virahol: ethylene glycol uncle butyl ether=6: 3: 1); stir, obtain photo-cured coating S30.
Spraying photo-cured coating S30 forms the thick coating of 18um on stainless steel substrate.
The base material of the surface being had coating places the F300 ultra-violet curing lamp system of FUSION company production to be cured, and condition of cure is wavelength 290-430nm, solidifies energy 1000mj/cm
2, be 25s set time.
Obtain sample S3.
Embodiment 4
Present embodiment is used to illustrate photo-cured coating disclosed by the invention and curing thereof.
With 3.2 weight part cellulose acetate butyrate color chips (CAB color chips, sun Chemical Corporation produces, median size is 70nm) with 70 weight part organic solvents (butylacetate is 1: 1 with the toluene by weight ratio), 80 weight part reactive monomer (dipentaerythritol acrylates, the SR399 that Sartomer company produces) mixes, stir, obtain containing the solution of tinting material.
With 50 weight part polyurethane acrylate resins (the 6154Q-80 resin that Changxing chemical company produces, 60 ℃ of following viscosity are 2000cps, functionality is 5.8), (BASF AG produces 50 weight part polyester acrylate resins, 60 ℃ of following viscosity are 2000cps, functionality is 2), 90 weight part reactive monomer (dipentaerythritol acrylates, the SR399 that Sartomer company produces) mixes with 90 weight part organic solvents (butylacetate is 1: 1 with the toluene by weight ratio), obtain containing the solution of matrix resin.
Above two kinds of solution are mixed; and add 36 weight part key light initiators (two (2; 4; 6-trimethoxy benzoyl)-(2; 4-two pentyloxy phenyl) phosphorus oxide; the IRGACURE 819 that Ciba company produces; activation wavelength is 380-420nm); 20 weight part fill-in light initiators (2-phenmethyl-2-dimethylamino-1-(4-morphine base phenyl)-butanone; the IRGACURE 369 that Ciba company produces; activation wavelength is 320-360nm); 1.5 weight part anti-settling agent (201P that moral modest company in Taiwan produces); 4 weight part dispersion agents (Kerper-602 that U.S. Kerper company produces); 60 weight part organic solvents (butylacetate is 1: 1 with the toluene by weight ratio); stir, obtain photo-cured coating S40.
Spraying photo-cured coating S40 forms the thick coating of 20um on stainless steel substrate.
The base material of the surface being had coating places the F300 ultra-violet curing lamp system of FUSION company production to be cured, and condition of cure is wavelength 300-430nm, solidifies energy 1100mj/cm
2, be 28s set time.
Obtain sample S4.
Embodiment 5
Present embodiment is used to illustrate photo-cured coating disclosed by the invention and curing thereof.
With 4 weight part cellulose acetate butyrate color chips (CAB color chips, sun Chemical Corporation produces, median size is 75nm) with 60 weight part organic solvents (butylacetate is 1: 1 with the toluene by weight ratio), 80 weight part reactive monomer (pentaerythritol triacrylates, the SR444 that Sartomer company produces) mixes, stir, obtain containing the solution of tinting material.
With the 100 weight part polyurethane acrylate resins (6158B-80 that Changxing chemical company produces, 60 ℃ of following viscosity are 2100cps, functionality is 5.2), 100 weight part reactive monomer (pentaerythritol triacrylates, the SR444 that Sartomer company produces) mixes with 90 weight part organic solvents (butylacetate is 1: 1 with the toluene by weight ratio), obtain containing the solution of matrix resin.
Above two kinds of solution are mixed; and add 42 weight part key light initiators (2; 4; 6-trimethylbenzoyl diphenyl phosphate oxidation; the DAROCUR 4265 that Ciba company produces; activation wavelength is 390-410nm); 16 weight part fill-in light initiators (2-phenmethyl-2-dimethylamino-1-(4-morphine base phenyl)-butanone; the IRGACURE 369 that Ciba company produces; activation wavelength is 330-365nm); 1.2 weight part anti-settling agent (moral modest company in Taiwan produce 229); 5 weight part dispersion agents (Kerper-630 that U.S. Kerper company produces); 1.4 weight part defoamer (EFKA2022 that Dutch Ai Fuka company produces); 1.0 weight part flow agent (EFKA3883 that Dutch Ai Fuka company produces); 60 weight part organic solvents (butylacetate is 1: 1 with the toluene by weight ratio); stir, obtain photo-cured coating S50.
Spraying photo-cured coating S50 forms the thick coating of 24um on plastic basis material.
The base material of the surface being had coating places the F300 ultra-violet curing lamp system of FUSION company production to be cured, and condition of cure is wavelength 310-430nm, solidifies energy 1200mj/cm
2, be 30s set time.
Obtain sample S5.
Embodiment 6
Present embodiment is used to illustrate photo-cured coating disclosed by the invention and curing thereof.
With 6 weight part cellulose acetate butyrate color chips (CAB color chips, sun Chemical Corporation produces, median size is 75nm) with ethylene glycol uncle butyl ether=6: 3: 1), 90 weight part reactive monomer (Viscoat 295s 60 weight part organic solvents (acetone: Virahol:, the SR351 that Sartomer company produces) mixes, stir, obtain containing the solution of tinting material.
With 50 weight part polyurethane acrylate resin (aliphatic urethane acrylates, the 611B-85 resin that Changxing chemical company produces, 60 ℃ of following viscosity are 1800cps, functionality is 5.6), the 50 weight part polyester acrylate resins (CN2254 that Sartomer company produces, 60 ℃ of following viscosity are 2000cps, functionality is 2), 90 weight part reactive monomer (Viscoat 295s, the SR351 that Sartomer company produces) with 90 weight part organic solvents (acetone: Virahol: ethylene glycol uncle butyl ether=6: 3: 1) mix, obtain containing the solution of matrix resin.
Above two kinds of solution are mixed, and add 45 weight part key light initiators (two (2,4,6-Three methyl Benzene formyl) phenyl phosphorus oxide, the DAROCUR 4265 that Ciba company produces, activation wavelength is 380-420nm), 18 weight part fill-in light initiators (2-methyl isophthalic acid (4-(methylthio group) phenyl)-2-morphine-1-acetone, the IRGACURE 907 that Ciba company produces, activation wavelength is 340-365nm), 1.2 weight part anti-settling agent (Japanese nanmu originally changes into the 6900-20X that company produces), 6 weight part dispersion agents (Kerper-605 that U.S. Kerper company produces), 1.2 weight part defoamer (EFKA2040 that Dutch Ai Fuka company produces), 1.0 weight part flow agent (DEGO410 that German Di Gao company produces), 60 weight part organic solvents (acetone: Virahol: ethylene glycol uncle butyl ether=6: 3: 1), stir, obtain photo-cured coating S60.
Spraying photo-cured coating S60 forms the thick coating of 20um on stainless steel substrate.
The base material of the surface being had coating places the F300 ultra-violet curing lamp system of FUSION company production to be cured, and condition of cure is wavelength 320-430nm, solidifies energy 1200mj/cm
2, be 30s set time.
Obtain sample S6.
Comparative Examples 1
This Comparative Examples is used for comparative illustration photo-cured coating disclosed by the invention and curing thereof.
The preparation method of photo-cured coating and sheet material is identical with embodiment 2, different is: adopt light trigger (2-hydroxy-2-methyl-1-phenyl-acetone, the DAROCUR BP that Ciba company produces, activation wavelength is 300-360nm) key light initiator in the alternative embodiment 2, adopt 7 weight part pigment (Degussa FW200) to replace the cellulose acetate butyrate color chips.
Obtain sample D1.
Comparative Examples 2
This Comparative Examples is used for comparative illustration photo-cured coating disclosed by the invention and curing thereof.
The preparation method of photo-cured coating and sheet material is identical with embodiment 2, and different is: adopt 7 weight part pigment (Degussa FW200) to replace the cellulose acetate butyrate color chips.
Obtain sample D2.
Comparative Examples 3
This Comparative Examples is used for comparative illustration photo-cured coating disclosed by the invention and curing thereof.
The preparation method of photo-cured coating and sheet material is identical with embodiment 6, and different is: adopt 6 weight part pigment (BASF L3885) to replace the cellulose acetate butyrate color chips.
Obtain sample D3.
Performance test
Above-mentioned sheet material S1-S6, the D1-D3 for preparing carried out following performance test:
1, sticking power test
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%.
2, hardness test
With reference to GB GB/T 6739-1996 " hardness of film pencil assay method ";
With 1H Mitsubishi pencil, with pencil sharper to exposing about cylindrical lead for retractable pencil 3mm length (attention can not damage pen core), holding pencil makes it become an angle of 90 degrees with No. 400 waterproof abrasive papers, on sand paper, do not stop to draw circle with friction pen core end face, when obtaining the sharp keen lead for retractable pencil of end face flat edges till (must not there be breakage and breach in the edge); Be contained on the special-purpose pencil hardness tester (load that is applied on the nib is 1kg, and the angle of pencil and horizontal plane is 45 °), promote pencil and grow, draw 5 (different positionss) altogether to the about 5mm of front slide, again with eraser with pencil trace wiped clean.
The result judges: checking that product surface has no marking (scratching finish paint), is qualified as 1 when following
3, the wear-resisting test of RCA
With the wear-resisting tester of NORMAN RCA of special use (model: 7-IBB-647) and special-purpose paper tape (11/16inch wide * 6 or 8inch diameter), apply the load of 175g, drive paper tape in 250 circulations of the surface of sample friction.
The result judges: it is qualified when not revealing the exact details (exposing ground) to paint that the back is finished in test
4, fixed temperature and humidity test
Product is placed on 70 ℃ ± 2 ℃ of temperature; Storage 48h under the constant-temperature constant-humidity environment of humidity 93% ± 2% places inspection product appearance in back more than the 2h under normal temperature environment after test is finished, and the sticking power of test paint.
The result judges: it is unusual that product surface does not have variable color, foaming, peeling paint etc., and it is above and be qualified when not having integral lattice and coming off that the sticking power test reaches 3B.
5, temperature shock test
Sample is put into thermal shock test chamber; Under-40 ℃ ± 2 ℃ low temperature environment, keep earlier 1h, in 1min, temperature switched under 70 ℃ ± 2 ℃ the hot environment and maintenance 1h, do 24 circulations (48h) altogether.After test is finished, check the outward appearance of product, and the sticking power of test paint.
The result judges: the outward appearance flawless of product, foaming, peeling paint etc. are unusual; It is above and be qualified when not having integral lattice and coming off that sticking power test reaches 3B.
6, neutral salt spray test
A, with sample cotton wiped clean.
B, sample are placed angle: 25 degree proofing box temperature: 35 ℃ of proofing box humidity: 〉=85%RH solution compolision: 5%NaCl pH value=6.8 spray times: the 2H laying temperature is: 40 ℃
Humidity: 〉=95% storage period: 168H
C, dry up, at room temperature placed 2 hours with normal temperature flushing with clean water 5 minutes and with blower.Criterion: the surface nothing comes off, and bubbles, and variable color etc. are unusual.
7, outward appearance
Whether even by visual inspection coating surface color, whether grow diming phenomenon appears.
Test result is charged to table 1.
Table 1
| Sample | Sticking power | Hardness | RCA is wear-resisting | Fixed temperature and humidity | Temperature shock | Neutral salt spray | Outward appearance |
| S1 | 4B | The 1H no marking | ≥250 | Do not have come off, variable color, foaming; Sticking power 3B | Do not have come off, variable color, foaming; Sticking power 3B | Do not have come off, variable color, foaming | Color even, nothing is grown dim |
| S2 | 4B | The 1H no marking | ≥250 | Do not have come off, variable color, foaming; Sticking power 3B | Do not have come off, variable color, foaming; Sticking power 3B | Do not have come off, variable color, foaming | Color even, nothing is grown dim |
| S3 | 5B | The 1H no marking | ≥250 | Do not have come off, variable color, foaming; Sticking power 4B | Do not have come off, variable color, foaming; Sticking power 4B | Do not have come off, variable color, foaming | Color even, nothing is grown dim |
| S4 | 5B | The 1H no marking | ≥250 | Do not have come off, variable color, foaming; Sticking power 4B | Do not have come off, variable color, foaming; Sticking power 4B | Do not have come off, variable color, foaming | Color even, nothing is grown dim |
| S5 | 5B | The 1H no marking | ≥250 | Do not have come off, variable color, foaming; Sticking power 4B | Do not have come off, variable color, foaming; Sticking power 4B | Do not have come off, variable color, foaming | Color even, nothing is grown dim |
| S6 | 5B | The 1H no marking | ≥250 | Do not have come off, variable color, foaming; Sticking power 5B | Do not have come off, variable color, foaming; Sticking power 5B | Do not have come off, variable color, foaming | Color even, nothing is grown dim |
| D1 | 1B | 1H has scuffing | 100 times show-through | Seriously bubble, come off | Cracking bubbles | The serious foaming | Shade differs |
| D2 | 2B | 1H has scuffing | 150 times show-through | Slightly bubble, come off | Slight cracking | The slight foaming | Shade differs |
| D3 | 3B | 1H has scuffing | 100 times show-through | Slightly bubble, come off | Slight cracking | The slight foaming | Shade differs |
From the test result of table 1 as can be seen: by the coating apparent property excellence that paint solidification disclosed by the invention obtains, color even does not have the phenomenon of growing dim.And the physicals of this coating is very excellent.Even thicker at rete, under the more situation of pigment, also can realize the abundant curing of coating, obtain the coating of excellent performance.
The above only is preferred embodiment of the present invention, not in order to restriction the present invention, all any modifications of being done within the spirit and principles in the present invention, is equal to and replaces and improvement etc., all should be included within protection scope of the present invention.
Claims (12)
1. photo-cured coating, comprise matrix resin, key light initiator, reactive monomer, tinting material and organic solvent, it is characterized in that described matrix resin contains polyurethane acrylate resin and/or polyester acrylate, the activation wavelength of described key light initiator is 380-430nm; Described tinting material is the cellulose acetate butyrate color chips.
2. photo-cured coating according to claim 1 is characterized in that, the median size of described cellulose acetate butyrate color chips is 50-100nm.
3. photo-cured coating according to claim 1 and 2 is characterized in that, described key light initiator is the phosphorus oxide photoinitiator.
4. photo-cured coating according to claim 3, it is characterized in that, with described matrix resin content is benchmark, described reactive monomer content is 150-200wt%, described key light initiator content is 25-50wt%, described colorant content is 2-8wt%, and described organic solvent content is 150-250wt%.
5. photo-cured coating according to claim 1 is characterized in that, described polyurethane acrylate resin is 500cps-4500cps 60 ℃ of following viscosity, and functionality is 4-6; Described polyester acrylate is 1300cps-4500cps 60 ℃ of following viscosity, and functionality is 2-4.
6. photo-cured coating according to claim 1 or 5 is characterized in that described matrix resin is polyurethane acrylate resin and polyester acrylate, and wherein, the content of polyurethane acrylate resin and polyester acrylate is than being 1.5-1: 1.
7. photo-cured coating according to claim 1, it is characterized in that select oneself in omega-diol diacrylate, tripropylene glycol diacrylate, pentaerythritol triacrylate, Viscoat 295, the dipentaerythritol acrylate one or more of described reactive monomer.
8. photo-cured coating according to claim 1 is characterized in that, also contains the fill-in light initiator in the described photo-cured coating, and the activation wavelength of described fill-in light initiator is 300-369nm.
9. photo-cured coating according to claim 8 is characterized in that, described fill-in light initiator is selected from one or more in alpha hydroxy ketone light trigger or the benzophenone-tertiary amines light trigger; With described matrix resin content is benchmark, and described fill-in light initiator content is 10-20wt%.
10. photo-cured coating according to claim 1 is characterized in that, also contains in flow agent, dispersion agent, defoamer, the anti-settling agent one or more in the described photo-cured coating; With described matrix resin content is benchmark, and described flow agent content is 0-2wt%, and described dispersant is 0-10wt%, and described antifoam content is 0-1.6wt%, and described anti-settling agent content is 0-2wt%.
11. the curing of a photo-cured coating comprises photo-cured coating is coated on the base material, is cured; Described condition of cure is: wavelength 280-450nm, solidify energy 800-1200mj/cm
2, be 20-30s set time; Wherein, described photo-cured coating is any described photo-cured coating among the claim 1-10.
12. curing according to claim 11 is characterized in that, photo-cured coating is coated on the base material, the coat-thickness of formation is 10-30um.
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| CN104937052A (en) * | 2012-12-20 | 2015-09-23 | 莫门蒂夫性能材料股份有限公司 | Radiation curable hardcoat with improved weatherability |
| CN106471027B (en) * | 2014-06-30 | 2019-02-05 | Dic株式会社 | Ultra-violet solidified composition |
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Application publication date: 20111019 |