CN101845243A - Low-energy electron beam radiation curing coating and use method thereof - Google Patents
Low-energy electron beam radiation curing coating and use method thereof Download PDFInfo
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Abstract
The invention discloses a low-energy electron beam radiation curing coating, which comprises the following components in percentage by weight: 40-90 percent of reactivity oligomer, 10-60 percent of reactivity monomer, 0.3-5 percent of additive, 0-30 percent of thermoplastic resin, 0-15 percent of photoinitiator and 0-30 percent of pigment and filler. The coating is particularly suitable for coating processing on substrate made of plastic or paper. A use method of the low-energy electron beam radiation curing coating comprises the following steps of: (a) printing at least one layer of the electron beam radiation curing coating on the plastic or paper substrate; (b) radiating the coating by adopting an electron beam of no more than 200+/-10kV; or repeating the use steps. The coating has low cost and good environment protection property. The coating obtained by using the low-energy electron beam radiation curing coating has good abrasive resistance, scratching resistance and solvent resistance.
Description
Technical field
The present invention relates to a kind of low-energy electron beam radiation curing coating and using method thereof, relate in particular to a kind of low-energy electron beam radiation curing coating and using method thereof that is applied on plastic cement or the paper ground.
Background technology
In the printing industry, ultraviolet light polymerization makes much progress now.In many low speed used to the printing in a narrow margin of middling speed, optical curing of UV was both economical working method.Yet when wealthy panel height print duplication was brushed, the heat that UV produces was many, makes printed coating inhomogeneous, and when base materials such as the film printing of some thermo-sensitivitys, film is yielding.Because the energy when the UV photo-cured coating solidifies is less, the residual more unreacted of the coating after the curing is small molecule monomer completely, owing to contain light trigger in the prescription, the migration composition in the coating is more simultaneously, and smell is bigger, and film performance is relatively poor.
Chinese patent CN101117458 discloses the coating material solidified of a kind of UV-light or electron beam initiation, in reactor, at first add vulcabond, catalyzer, among the polyurethane polyol adding reactor with equivalent, its adding speed should be controlled at the mixture temperature that makes in the reactor and be no more than 80 ℃, continue reactor heating, make reaction mixture be incubated 2 hours down at 65 ℃, then with the disposable adding of 2-hydroxyl acrylic ethyl ester of equivalent, and under 65 ℃, be incubated 1 hour again, generate prepolymer, get prepolymer 20kg, reactive thinner with 80kg, light trigger, thermo-stabilizer, the selectivity adhesion promoters adds, continue to be incubated 2 hours down, promptly make coating at 65 ℃.
Summary of the invention
The technical problem to be solved in the present invention provides another kind of low-energy electron beam radiation curing coating, and further, the present invention also provides the using method of this coating.
For solving above technical problem, the technical solution adopted in the present invention is: a kind of low-energy electron beam radiation curing coating, its weight percent consist of the additive of 40%-90% reactive oligomers, 10%-60% reactive monomer, 0.3%-5%, the thermoplastic resin of 0%-30%, the light trigger of 0%-15%, the color stuffing of 0%-30%.
Further: in above-mentioned electron beam radiation cured coating, described reactive oligomers is acrylate or methacrylic ester functional group's a oligopolymer.
Described reactive monomer is three and a tetraacrylate of tetramethylolmethane, three and tetraacrylate of alkoxide tetramethylolmethane, diacrylate tripropylene glycol ester, alkoxide diacrylate tripropylene glycol ester, dipropylene glycol diacrylate, the alkoxide dipropylene glycol diacrylate, Viscoat 295, the alkoxide Viscoat 295, Ethyl acrylate, 2-EHA, isobornyl acrylate, decyl acrylate, lauryl acrylate, octadecyl acrylate, vinylformic acid 2-ethoxy ethyl ester, the lauryl vinyl ether, 2-ethylhexyl vinyl ether, the n-vinyl formamide, isodecyl acrylate, vinyl-hexanolactam, Isooctyl acrylate monomer and N-vinyl pyrrolidone, ethylene glycol phenyl ether-acrylate, polyoxyethylene glycol phenyl ether-acrylate, one or more in the phenyl derivatives that the alkyl of polypropylene glycol phenyl ether-acrylate and these compounds replaces.
Described thermoplastic resin is one or more in rosin and derivative thereof, petroleum resin, dammar gum, polyacrylic resin, polyvinyl chloride (PVC) RESINS, resol, vibrin, the polyamide resin.
Described light trigger is a radical photoinitiator, comprises hydroxycyclohexylphenylketone, hydroxymethyl phenyl acetone, dimethoxy benzene benzoylformaldoxime, 2-methyl isophthalic acid-[4 (methyl sulfo-) phenyl] 2-morpholino acetone-1; 1-(4-isopropyl phenyl)-2-hydroxy-2-methyl third-1-ketone, 1-(4-dodecyl-phenyl)-2 hydroxy-2-methyl third-1-ketone, 4-(2-hydroxyl-oxethyl) phenyl-2-(2-hydroxyl-2-propyl group) ketone, diethoxybenzene benzoylformaldoxime, 2; 4; 6-trimethylbenzoyl phenylbenzene dioxy phosphorus ketone, (2; 6-dimethoxy benzoyl)-2; 4, mixture of 4-tri-methyl-amyl phosphine oxide and 2-hydroxy-2-methyl-1-phenyl-third-1-ketone and composition thereof.
Described additive is stablizer, adhesion promoter, photosensitizers, the catalyzer that those skilled in the art use always, one or more in initiator, lubricant, wetting agent, flow agent, defoamer, oxidation inhibitor and the dispersion agent.
Described color stuffing is titanium dioxide, zinc oxide, zinc sulphide, barium sulfate, pure aluminium silicate, Calucium Silicate powder, carbon black, iron oxide black, black, the ferric oxide of copper chromite, chromoxide green, iron orchid, chrome green, manganese violet, cobaltous phosphate, lead chromate, lead molybdate, with cadmium, titanate, pearling agent, talcum powder, lime carbonate, aluminum oxide, kaolin, monoazo pigment. diazo pigment, diazonium contract and give up pigment, dihydroketoacridine pigment, dioxazine violet. vat pigment, one or more in thioindigo color, phthalocyanine pigment, the tetrachloroisoindolinone.
Further again, it is using method on the ground that the present invention also provides above-mentioned electron beam radiation cured coating to be printed on plastic cement or paper.In this using method, when electron beam radiation cured coating did not contain light trigger, it uses step was a) to be printed in plastic cement or the paper ground electron beam radiation cured coating of one deck at least; B) employing is less than or equal to the above-mentioned coating of 200 ± 10kV electron beam irradiation; Perhaps repeat above-mentioned use step.
In another kind of using method, when electron beam radiation cured coating contained a spot of light trigger, it uses step was a) to be printed in plastic cement or the paper ground electron beam radiation cured coating of one deck at least; B) adopt UV-light to carry out the Procuring coating earlier; C) employing is less than or equal to the above-mentioned coating of 200 ± 10kV electron beam irradiation again; Perhaps repeat above-mentioned use step.
Above-mentioned electron beam radiation cured coating does not contain volatile organic matter, and the solidified energy is big, make coating curing more thorough, substantially not residual small molecule monomer, so no matter be coating, still the coating after solidifying, all more environmental protection and safety are particularly suitable for the application of packaged products such as food, cigarette, drinks.Coating curing is more thorough, and coating has physical and chemical performances such as higher wear resistance, scratch resistance, solvent resistance.Simultaneously owing to do not contain or seldom contain light trigger, so coating also has excellent yellowing resistance, and good snappiness.And for thick coating and the coating that contains pigments system, EB solidifies can show its superiority especially biglyyer.EB solidified energy is bigger, so can obtain higher curing speed, print speed can be up to 3000 feet per minute clocks.EB coating does not need the higher light trigger of price, so lower with respect to UV coating cost.Utilize EB solidify to produce these characteristics of less calories, the temperature-sensitive printing material that can be difficult to tackle to the UV printing prints and is coated with processing as heat-shrinkable film, heat sensitive paper etc.
Embodiment
Purport of the present invention is to adjust system component and proportioning, makes coating not contain volatile organic matter, lacks usefulness or without light trigger, makes coating have the higher feature of environmental protection.Because coating curing energy height makes coating curing more thorough, not residual substantially small molecule monomer, coating has physical and chemical performances such as higher wear resistance, scratch resistance, solvent resistance.Coating owing to coating does not contain or contains less small-molecule substances such as light trigger simultaneously, so coating also has excellent yellowing resistance, and good snappiness.And for thick coating and the coating that contains pigments system, EB solidifies can show its superiority especially biglyyer.Because light trigger price height, this coating is used or less without the higher light trigger of price, so lower with respect to optical curing of UV coating cost.Utilize EB solidify to produce these characteristics of less calories, can print the temperature-sensitive printing material that the printing of UV coating is difficult to tackle and be coated with processing, as heat-shrinkable film, heat sensitive paper etc.Below in conjunction with embodiment content of the present invention is described in further detail, mentioned content is not a limitation of the invention among the embodiment, and the selection of material and condition can be suited measures to local conditions and the result be there is no substantial effect in the method.
At first sketch general planning of the present invention: a kind of low-energy electron beam radiation curing coating, its weight percent consist of the additive of 40%-90% reactive oligomers, 10%-60% reactive monomer, 0.3%-5%, the thermoplastic resin of 0%-30%, the light trigger of 0%-15%, the color stuffing of 0%-30%.
It is use on the ground that above-mentioned electron beam radiation cured coating is printed on plastic cement or paper.The use step is a) to be printed in plastic cement or the paper ground coating of the electron beam radiation cured coating of one deck at least; B) employing is less than or equal to the above-mentioned coating of 200 ± 10kV electron beam irradiation; Perhaps repeat above-mentioned use step.
When coating contained light trigger less, described use step was a) to be printed in plastic cement or the paper ground coating of the electron beam radiation cured coating of one deck at least; B) can adopt UV-light to carry out the Procuring coating earlier; C) employing is less than or equal to the above-mentioned coating of 200 ± 10kV electron beam irradiation again; Perhaps repeat above-mentioned use step.
Embodiment 1
The preparation electron beam curable coatings, with reactive oligomers 1500 gram epoxy acrylate oligomers, 300 gram urethane acrylate oligomers, 300 gram polyester acrylate oligomers, reactive monomer 1000 gram diacrylate tripropylene glycol ester TPGDA, 350 gram Viscoat 295 TMPTA, leveling auxiliary agent 15 gram Organosiliconcopolymere BYK333 mix.
Roller coat is in paper surface, and about 4 microns of coating thickness is exposed in the electron beam irradiation of 150kV, and the about 60kGy of dosage is cured sample.The coating abrasion performance of gained, scratch resistance, solvent resistance are good.
Embodiment 2
The preparation electron beam curable coatings, with reactive oligomers 1500 gram methacrylic ester oligomers, 300 gram urethane acrylate oligomers, 300 gram polyester acrylate oligomers, reactive monomer 1000 gram Viscoat 295s, 350 gram Viscoat 295 TMPTA, leveling auxiliary agent 15 gram Organosiliconcopolymere BYK333 mix.
Roller coat is in paper surface, and about 4 microns of coating thickness is exposed in the electron beam irradiation of 180kV, and the about 60kGy of dosage is cured sample.The coating abrasion performance of gained, scratch resistance, solvent resistance are good.
Embodiment 3
The preparation electron beam curable coatings, with reactive oligomers 1500 gram methacrylic ester oligomers, 300 gram urethane acrylate oligomers, 300 gram polyester acrylate oligomers, reactive monomer 1000 gram Ethyl acrylate, 350 gram Viscoat 295 TMPTA, leveling auxiliary agent 15 gram Organosiliconcopolymere BYK333 mix.
Roller coat is in paper surface, and about 4 microns of coating thickness is exposed in the electron beam irradiation of 200kV, and the about 60kGy of dosage is cured sample.The coating abrasion performance of gained, scratch resistance, solvent resistance are good.
Embodiment 4
The blackwash of preparation electrocuring, with reactive oligomers 2000 gram epoxy acrylate oligomers, 300 gram urethane acrylate oligomers, 300 gram polyester acrylate oligomers, reactive monomer 500 gram diacrylate tripropylene glycol ester TPGDA, 500 gram Viscoat 295 TMPTA, leveling auxiliary agent 15 gram Organosiliconcopolymere BYK333, wetting dispersing agent 40 gram dispersant B YK163,400 gram carbon blacks mix.
Curing mode is with example 1.The coating abrasion performance of gained, scratch resistance, solvent resistance are good.
Embodiment 5
The whitewash of preparation electrocuring, with reactive oligomers 2000 gram epoxy acrylate oligomers, 300 gram urethane acrylate oligomers, 300 gram polyester acrylate oligomers, reactive monomer 500 gram diacrylate tripropylene glycol ester TPGDA, 500 gram Viscoat 295 TMPTA, leveling auxiliary agent 15 gram Organosiliconcopolymere BYK333, wetting dispersing agent 40 gram dispersant B YK163,800 gram titanium dioxides mix.Curing mode is with example 1.The coating abrasion performance of gained, scratch resistance, solvent resistance are good.
Embodiment 6
The whitewash of preparation electrocuring; with reactive oligomers 2000 gram methacrylic ester oligomers, 300 gram urethane acrylate oligomers, 300 gram polyester acrylate oligomers; reactive monomer 500 gram diacrylate tripropylene glycol ester TPGDA, 500 gram Viscoat 295 TMPTA; 100 grams 2; 4; 6-trimethylbenzoyl phenylbenzene dioxy phosphorus ketone; leveling auxiliary agent 15 gram Organosiliconcopolymere BYK333; wetting dispersing agent 40 gram dispersant B YK163,800 gram titanium dioxides mix.
Roller coat is in paper surface, and about 4 microns of coating thickness adopts UV-light to carry out the Procuring coating earlier; Be exposed in the electron beam irradiation of 200kV, the about 60kGy of dosage is cured sample again.The coating abrasion performance of gained, scratch resistance, solvent resistance are good.
In the above-described embodiments, described reactive monomer can also be three and a tetraacrylate of tetramethylolmethane, three and tetraacrylate of alkoxide tetramethylolmethane, diacrylate tripropylene glycol ester, alkoxide diacrylate tripropylene glycol ester, dipropylene glycol diacrylate, the alkoxide dipropylene glycol diacrylate, Viscoat 295, the alkoxide Viscoat 295, Ethyl acrylate, 2-EHA, isobornyl acrylate, decyl acrylate, lauryl acrylate, octadecyl acrylate, vinylformic acid 2-ethoxy ethyl ester, the lauryl vinyl ether, 2-ethylhexyl vinyl ether, the n-vinyl formamide, isodecyl acrylate, vinyl-hexanolactam, Isooctyl acrylate monomer and N-vinyl pyrrolidone, ethylene glycol phenyl ether-acrylate, polyoxyethylene glycol phenyl ether-acrylate, one or more in polypropylene glycol phenyl ether-acrylate.
Described additive is stablizer, adhesion promoter, photosensitizers, the catalyzer that the art technology important official uses always, one or more in initiator, lubricant, wetting agent, flow agent, defoamer, oxidation inhibitor and the dispersion agent
Described thermoplastic resin is one or more in rosin, petroleum resin, dammar gum, polyacrylic resin, polyvinyl chloride (PVC) RESINS, resol, vibrin, the polyamide resin.
Described light trigger is a radical photoinitiator, and described radical photoinitiator is hydroxycyclohexylphenylketone, hydroxymethyl phenyl acetone, dimethoxy benzene benzoylformaldoxime, 2-methyl isophthalic acid-[4 (methyl sulfo-) phenyl] 2-morpholino acetone-1; 1-(4-isopropyl phenyl)-2-hydroxy-2-methyl third-1-ketone, 1-(4-dodecyl-phenyl)-2 hydroxy-2-methyl third-1-ketone, 4-(2-hydroxyl-oxethyl) phenyl-2-(2-hydroxyl-2-propyl group) ketone, diethoxybenzene benzoylformaldoxime, 2; 4; 6-trimethylbenzoyl phenylbenzene dioxy phosphorus ketone, (2; 6-dimethoxy benzoyl)-2; 4, one or more mixtures in 4-tri-methyl-amyl phosphine oxide and the 2-hydroxy-2-methyl-1-phenyl-third-1-ketone.
Described color stuffing is titanium dioxide, zinc oxide, zinc sulphide, barium sulfate, pure aluminium silicate, Calucium Silicate powder, carbon black, iron oxide black, black, the ferric oxide of copper chromite, chromoxide green, iron orchid, chrome green, manganese violet, cobaltous phosphate, lead chromate, lead molybdate, with cadmium, titanate, pearling agent, talcum powder, lime carbonate, aluminum oxide, kaolin, monoazo pigment, diazo pigment, diazonium contract house pigment, dihydroketoacridine pigment, dioxazine violet, vat pigment, one or more in thioindigo color, phthalocyanine pigment, the tetrachloroisoindolinone.
Claims (10)
1. low-energy electron beam radiation curing coating, its weight percent consists of the additive of 40%-90% reactive oligomers, 10%-60% reactive monomer, 0.3%-5%, the thermoplastic resin of 0%-30%, the light trigger of 0%-15%, the color stuffing of 0%-30%.
2. low-energy electron beam radiation curing coating according to claim 1 is characterized in that: described reactive oligomers is acrylate or methacrylic ester functional group's a oligopolymer.
3. low-energy electron beam radiation curing coating according to claim 2, it is characterized in that: described reactive monomer is three and a tetraacrylate of tetramethylolmethane, three and tetraacrylate of alkoxide tetramethylolmethane, diacrylate tripropylene glycol ester, alkoxide diacrylate tripropylene glycol ester, dipropylene glycol diacrylate, the alkoxide dipropylene glycol diacrylate, Viscoat 295, the alkoxide Viscoat 295, Ethyl acrylate, 2-EHA, isobornyl acrylate, decyl acrylate, lauryl acrylate, octadecyl acrylate, vinylformic acid 2-ethoxy ethyl ester, the lauryl vinyl ether, 2-ethylhexyl vinyl ether, the n-vinyl formamide, isodecyl acrylate, vinyl-hexanolactam, Isooctyl acrylate monomer and N-vinyl pyrrolidone, ethylene glycol phenyl ether-acrylate, polyoxyethylene glycol phenyl ether-acrylate, one or more in polypropylene glycol phenyl ether-acrylate.
4. low-energy electron beam radiation curing coating according to claim 3, it is characterized in that: described additive is stablizer, adhesion promoter, photosensitizers, catalyzer, one or more in initiator, lubricant, wetting agent, flow agent, defoamer, oxidation inhibitor and the dispersion agent
5. low-energy electron beam radiation curing coating according to claim 4 is characterized in that: described thermoplastic resin is one or more in rosin, petroleum resin, dammar gum, polyacrylic resin, polyvinyl chloride (PVC) RESINS, resol, vibrin, the polyamide resin.
6. low-energy electron beam radiation curing coating according to claim 5, it is characterized in that: described light trigger is a radical photoinitiator, and described radical photoinitiator is hydroxycyclohexylphenylketone, hydroxymethyl phenyl acetone, dimethoxy benzene benzoylformaldoxime, 2-methyl isophthalic acid-[4 (methyl sulfo-) phenyl] 2-morpholino acetone-1; 1-(4-isopropyl phenyl)-2-hydroxy-2-methyl third-1-ketone, 1-(4-dodecyl-phenyl)-2 hydroxy-2-methyl third-1-ketone, 4-(2-hydroxyl-oxethyl) phenyl-2-(2-hydroxyl-2-propyl group) ketone, diethoxybenzene benzoylformaldoxime, 2; 4; 6-trimethylbenzoyl phenylbenzene dioxy phosphorus ketone, (2; 6-dimethoxy benzoyl)-2; 4, one or more mixtures in 4-tri-methyl-amyl phosphine oxide and the 2-hydroxy-2-methyl-1-phenyl-third-1-ketone.
7. coating according to claim 6, it is characterized in that: described color stuffing is a titanium dioxide, zinc oxide, zinc sulphide, barium sulfate, pure aluminium silicate, Calucium Silicate powder, carbon black, iron oxide black, the copper chromite is black, ferric oxide, chromoxide green, the iron orchid, chrome green, manganese violet, cobaltous phosphate, lead chromate, lead molybdate, and cadmium, titanate, pearling agent, talcum powder, lime carbonate, aluminum oxide, kaolin, monoazo pigment, diazo pigment, the diazonium house pigment that contracts, dihydroketoacridine pigment dioxazine violet, vat pigment, thioindigo color, phthalocyanine pigment, in the tetrachloroisoindolinone one or more.
One kind to be printed on plastic cement or paper according to each described low-energy electron beam radiation curing coating among the claim 1-7 be use on the ground.
9. using method according to claim 8 is characterized in that: use step to be,
A) be printed in plastic cement or the paper ground coating of the electron beam radiation cured coating of one deck at least;
B) employing is less than or equal to the above-mentioned coating of 200 ± 10kV electron beam irradiation;
Perhaps repeat above-mentioned use step.
10. using method according to claim 8 is characterized in that: use step to be,
A) be printed in plastic cement or the paper ground coating of the electron beam radiation cured coating of one deck at least;
B) can adopt UV-light to carry out the Procuring coating earlier;
C) employing is less than or equal to the above-mentioned coating of 200 ± 10kV electron beam irradiation again;
Perhaps repeat above-mentioned use step.
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