CN101423676A - Method for preparing non-toxic visible ultraviolet heat insulating UV coating material - Google Patents
Method for preparing non-toxic visible ultraviolet heat insulating UV coating material Download PDFInfo
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- CN101423676A CN101423676A CNA2008102439639A CN200810243963A CN101423676A CN 101423676 A CN101423676 A CN 101423676A CN A2008102439639 A CNA2008102439639 A CN A2008102439639A CN 200810243963 A CN200810243963 A CN 200810243963A CN 101423676 A CN101423676 A CN 101423676A
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Abstract
The invention relates to a method for preparing a nontoxic visible ultraviolet and heat insulation UV coating for food packaging and belongs to a composite material for packaging and the field of a photocuring technology. The invention relates to a white carbon black and metal doped tin oxide nanometer powder body composite ultraviolet photo-cured coating which can improve the capacity of ultraviolet insulation and heat insulation; the coating mainly comprises a photosensitive oligomer, an active thinner, a light evocating agent, white carbon black and metal doped tin oxide, a filler and an additive. The UV coating material has innocuity and harmlessness, can obstruct ultraviolet light of over 97 percent and infrared light of over 80 percent in daylight, has functions of transparence, heat insulation, sterilization and uneasy gleization, is in particular suitable for a visible plastic food packaging bag, a transparent polyester food vessel and the like, is convenient to keep food fresh and store food, prolongs guarantee period of food and reduces the deterioration and waste of food. The UV coating is not added with an organic solvent, is favorable for environmental protection, and has convenient construction and obvious environmental, social and economic benefits.
Description
Technical field
A kind of preparation method of non-toxic visible ultraviolet heat insulating UV coating relates to a kind of food bag that can be used for, and the photocuring visible ultraviolet heat insulating coating of packing such as food plastic container occasion belongs to composite material for packaging and photocuring technology field.
Background technology
Ultraviolet ray is a kind of radiation of wavelength 100～400 nanometers, and the ultraviolet ray in the daily life is mainly from sunlight, houselights.Ultraviolet light wave length, energy height a little less than the penetration power, are absorbed by body surface easily and are converted into interior energy, play an important role at the weathering process medium ultraviolet light of material, and a large amount of plastics, rubber are because UV-light reduces work-ing life greatly; Grease and containing in the fatty foods because greasy unsaturated, lipid acid deterioration by oxidation very easily under light action, and a large amount of addings of oxidation inhibitor, preservation agent etc. are harmful.Therefore non-toxic visible ultraviolet heat insulating UV coating is prepared into emphasis in order to study.
Summary of the invention
The purpose of this invention is to provide a kind of preparation of used for packing foods visible ultraviolet heat insulating UV coating, select the superfine white carbon black (hydrated SiO 2) of Meteorological Act preparation for use, metal-doped stannic oxide nano powder be equipped with the compound preparation of photosensitive oligomer a kind of have nontoxic, every ultraviolet, heat insulation ultraviolet-curing paint.
Technical scheme of the present invention:
A kind of non-toxic visible ultraviolet heat insulating UV coating, (%) is as follows for the composition of each component and weight percent:
Photosensitive oligomer 40～60
Reactive thinner 28～42
Light trigger 3～9
White carbon black 0.5～3
Metal-doped stannic oxide nano powder 1～5
Auxiliary agent 1～1.5
Described photosensitive oligomer is selected for use: one or more in hyperbranched polyester acrylic ester quasi-oligomer, ultra-branched polyurethane acrylate quasi-oligomer, epoxy acrylic oligoesters, urethane acrylate quasi-oligomer, the polyester acrylic oligoesters are provided by Jiangsu Miki Group;
Described reactive thinner is selected for use: hyperbranched polyester acrylic ester quasi-oligomer, ultra-branched polyurethane acrylate quasi-oligomer, tripropylene glycol diacrylate, Viscoat 295,1, in 6-hexanediyl ester, pentaerythritol triacrylate, neopentylglycol diacrylate, the Isooctyl acrylate monomer two kinds or several, provide by pool, last Hainan chemical industry;
Described light trigger is benzophenones/amines system, benzil two ketals, Benzoin ethyl ether, 1-hydroxyl-phenylcyclohexane ethyl ketone, α, in alpha-alpha-dimethyl-α hydroxy acetophenone, the thioxanthones one or more are provided by Tianjin Jiuri Chemical Industry Co., Ltd.;
Described white carbon black is the Meteorological Act preparation, and diameter range is 5～20nm, and Xi Meng chemical industry company limited provides by Shanghai, carries out the surface modification treatment mistake through silane coupling agent or titanate coupling agent, and silane coupling agent and titanate coupling agent are raised the chemical plant by the sky and provided;
Described metal-doped stannic oxide nano powder is a solid-phase synthesis, liquid-phase coprecipitation and combustion method synthetic one or more; Described metal is one or more in iron, zinc, aluminium, the antimony;
Described auxiliary agent comprises wetting dispersing agent, anti-settling agent, flow agent and defoamer.Wetting dispersing agent is the derivatives class of polymer unsaturated polyester carboxylic-acid or poly carboxylic acid/amine; Anti-settling agent is organobentonite class or polyethylene wax; Flow agent is silicone based or polyacrylate(s); Defoamer is silicone based.
The preparation method of described non-toxic visible ultraviolet heat insulating UV coating:
Composition and weight percent according to described each component, in mixing tank, press the reactive thinner in the described proportioning adding component earlier, wetting dispersing agent mixes, add gradually while stirring through surface-treated white carbon black, by rotating speed is that 300～23000 rev/mins high speed dispersion clarifixator is uniformly dispersed, add metal-doped stannic oxide nano powder, high speed dispersion is even, add photosensitive oligomer then, anti-settling agent in the auxiliary agent, flow agent and defoamer, adding light trigger again continues to mix, homodisperse, packing promptly makes non-toxic visible ultraviolet heat insulating UV coating.
Beneficial effect of the present invention:
Non-toxic visible ultraviolet heat insulating UV coating and decorating material of the present invention is nontoxic, can intercept UV-light more than 97% in the daylight and 80% above infrared rays, has transparent, heat insulation, sterilization, is difficult for the function of sticking ash.Be particularly suitable for visual plastic packing bag, transparent polyester food product containers etc., so that fresh-keeping, the storage of food, reduce the rotten waste of food at the quality guaranteed period of prolongation food.Non-toxic visible ultraviolet heat insulating UV coating of the present invention does not add organic solvent, adopt the coating composition of hyperbranched quasi-oligomer preparation need not add thinner, help environmental protection, and easy construction, tangible environmental benefit, social benefit and economic benefit had.
Embodiment
Embodiment 1
The coupling processing of white carbon black:
The white carbon black of the Meteorological Act of buying preparation is added silane coupling agent or the titanate coupling agent of its quality 0.2%-1%, add an amount of ethanol wetting, grind the dispersion surface modification treatment.
Embodiment 2
The preparation of metal-doped stannic oxide nano powder:
Adopt solid-phase synthesis to prepare metal-doped stannic oxide nano powder: to take by weighing Fe respectively by certain mol proportion
3O
4And SnO
2, Al
2O
3And SnO
2, ZnO and SnO
2, Sb
2O
3And SnO
2, acetone dispersion, ball milling, the oven dry of adding appropriate amount in 600～1100 ℃ of calcinings, obtain the light blue powder that does not wait to mazarine.
Adopt liquid-phase coprecipitation to prepare metal-doped stannic oxide nano powder: to take by weighing Fe respectively by certain mol proportion
3O
4And SnO
2, Al
2O
3And SnO
2, ZnO and SnO
2, Sb
2O
3And SnO
2,, be that precipitation agent carries out neutralization reaction and obtains precipitation with ammoniacal liquor with HCl dissolving.To washing of precipitate, suction filtration, oven dry, 850 ℃ of calcinings, obtain nano-powder.
Adopt combustion method to prepare metal-doped stannic oxide nano powder: to take by weighing Fe respectively by certain mol proportion
3O
4And SnO
2, Al
2O
3And SnO
2, ZnO and SnO
2, Sb
2O
3And SnO
2, each metal oxide and SnO
2The mole proportioning be 1: 7-1: 10 mix.With mol ratio is that 1: 7 nitric acid and citric acid is dissolved in deionized water, adds above-mentioned metal oxide heating for dissolving, with volume ratio be 1: 1 ammonia soln be added drop-wise in the above-mentioned solution to the pH value be 7, obtain the nattierblue stabilizing solution.Place baking oven in 100 ℃ of removal moisture this solution, solution progressively forms colloidal sol, gel in moisture evaporation.Gel is transferred in the retort furnace with 300 ℃ of thermal treatments, and gel expands gradually, forms a large amount of grey black porous flosss at last.This floss is continued to obtain light blue metal-doped stannic oxide nano powder 600 ℃ of roastings, and the performance after it is mixed compares See table 1.
It is best that above-mentioned nano-powder adopts combustion method to prepare the gained particles dispersed, and the powder characteristic of preparation is compared as follows that (uv transmittance records by ultraviolet-spectrophotometer, 100%-transmitance=rejection rate; Temperature head is shone under tungsten lamp relatively with blank ground by the back of filming at ground):
The performance that table 1 combustion method prepares metal-doped stannic oxide nano powder compares
The result shows that to adopt the adulterated ultraviolet-resistant effect of metallic antimony best, and heat-proof quality is better, but metallic antimony costs an arm and a leg, and what cost performance was the highest is metallic iron.
Embodiment 3
A kind of non-toxic visible ultraviolet heat insulating UV coating, by weight percentage: by urethane acrylate oligomer 25%, epoxy acrylate oligomer 20%, tripropylene glycol diacrylate 20%, Viscoat 295 12%, 1,6-hexanediyl ester 9%, white carbon black 3% adopts Sb
2O
3: SnO
2Be 1: 9 metal-doped stannic oxide nano powder 5%, 1-hydroxyl-phenylcyclohexane ethyl ketone 4.5%, wetting dispersing agent 0.4%, anti-settling agent 0.6%, flow agent 0.3%, defoamer 0.2% is formulated.The preparation method is with above-mentioned.Ultraviolet-resistant rate 97% after gained coating is filmed, 5 ℃ of the temperature difference.
Embodiment 4
A kind of non-toxic visible ultraviolet heat insulating UV coating, by weight percentage: by urethane acrylate oligomer 50%, tripropylene glycol diacrylate 10%, neopentylglycol diacrylate 9%, Viscoat 295 10%, Isooctyl acrylate monomer 9%, white carbon black 1% adopts Fe
3O
4: SnO
2Be 1: 9 metal-doped stannic oxide nano powder 5%, α, alpha-alpha-dimethyl-α hydroxy acetophenone 5%, wetting dispersing agent 0.2%, anti-settling agent 0.4%, flow agent 0.2%, defoamer 0.2% is formulated.The preparation method is with above-mentioned.Ultraviolet-resistant rate 60% after gained coating is filmed, 6 ℃ of the temperature difference.
Embodiment 5
A kind of non-toxic visible ultraviolet heat insulating UV coating, by weight percentage: by super branched polyurethane 85%, white carbon black 2% adopts Al
2O
3: SnO
2Be 1: 10 metal-doped stannic oxide nano powder 5%, benzophenone 3%, tertiary amine acrylate 2%, α, alpha-alpha-dimethyl-α hydroxy acetophenone 2%, wetting dispersing agent 0.2%, anti-settling agent 0.4%, flow agent 0.2%, defoamer 0.2% is formulated.The preparation method is with above-mentioned.Ultraviolet-resistant rate 42% after gained coating is filmed, 3 ℃ of the temperature difference.
Embodiment 6
A kind of non-toxic visible ultraviolet heat insulating UV coating, by weight percentage: by hyper-branched polyester 90%, white carbon black 1% adopts ZnO:SnO
2Be 1: 8 metal-doped stannic oxide nano powder 5%, benzil two ketals 3%, wetting dispersing agent 0.2%, anti-settling agent 0.35%, flow agent 0.25%, defoamer 0.2% is formulated.The preparation method is with above-mentioned.Ultraviolet-resistant rate 47% after gained coating is filmed, 3 ℃ of the temperature difference.
Claims (2)
1, a kind of non-toxic visible ultraviolet heat insulating UV coating is characterized in that the composition of each component and weight percent are as follows:
Photosensitive oligomer 40～60
Reactive thinner 28～42
Light trigger 3～9
White carbon black 0.5～3
Metal-doped stannic oxide nano powder 1～5
Auxiliary agent 1～1.5
Described photosensitive oligomer is selected for use: one or more in hyperbranched polyester acrylic ester quasi-oligomer, ultra-branched polyurethane acrylate quasi-oligomer, epoxy acrylic oligoesters, urethane acrylate quasi-oligomer, the polyester acrylic oligoesters;
Described reactive thinner is selected for use: in hyperbranched polyester acrylic ester quasi-oligomer, ultra-branched polyurethane acrylate quasi-oligomer, tripropylene glycol diacrylate, Viscoat 295,1,6 hexanediol diacrylate, pentaerythritol triacrylate, neopentylglycol diacrylate, the Isooctyl acrylate monomer two kinds or several;
Described light trigger is selected for use: benzophenones/amines system, benzil two ketals, Benzoin ethyl ether, 1-hydroxyl-phenylcyclohexane ethyl ketone, α, one or more in alpha-alpha-dimethyl-α hydroxy acetophenone, the thioxanthones;
Described white carbon black is: Meteorological Act preparation, diameter range is 5～20nm, by silane coupling agent or titanate coupling agent through the surface modification treatment mistake;
Described metal-doped stannic oxide nano powder is: solid-phase synthesis, liquid-phase coprecipitation and combustion method synthetic one or more; The used metal that mixes is selected for use: one or more in iron, zinc, aluminium, the antimony;
Described auxiliary agent is: wetting dispersing agent, anti-settling agent, flow agent and defoamer; Wetting dispersing agent is the derivatives class of polymer unsaturated polyester carboxylic-acid or poly carboxylic acid/amine; Anti-settling agent is organobentonite class or polyethylene wax; Flow agent is silicone based or polyacrylate(s); Defoamer is silicone based.
2, the preparation of the described non-toxic visible ultraviolet heat insulating UV coating of a kind of claim 1, it is characterized in that: according to the composition and the weight percent of described each component, in mixing tank, press the reactive thinner in the proportioning adding component earlier, wetting dispersing agent mixes, add gradually while stirring through surface-treated white carbon black, by rotating speed is that 300～23000 rev/mins high speed dispersion clarifixator is uniformly dispersed, add metal-doped stannic oxide nano powder, high speed dispersion is even, add photosensitive oligomer then, anti-settling agent in the auxiliary agent, flow agent and defoamer, adding light trigger again continues to mix, homodisperse, packing promptly makes non-toxic visible ultraviolet heat insulating UV coating.
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|---|---|---|---|
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| CN101423676B CN101423676B (en) | 2011-07-20 |
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| CN102260358A (en) * | 2010-05-31 | 2011-11-30 | 江苏英力科技发展有限公司 | Use of 2-methoxy-4'-benzoylbiphenyl as photoinitiator |
| CN101619179B (en) * | 2009-07-24 | 2012-03-21 | 江苏科技大学 | UV solidified light guide plate printing ink |
| CN102408765A (en) * | 2010-12-31 | 2012-04-11 | 深圳鼎好光化科技有限公司 | Ultraviolet ray and electron beam cured heat insulation coating |
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| CN103602222A (en) * | 2013-10-20 | 2014-02-26 | 安徽嘉木橡塑工业有限公司 | Ultraviolet heat insulation UV paint for packaging bag |
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| CN103602222A (en) * | 2013-10-20 | 2014-02-26 | 安徽嘉木橡塑工业有限公司 | Ultraviolet heat insulation UV paint for packaging bag |
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