CN104175663B - A kind of ultraviolet radiation preventing transparency high separation thin film and application thereof - Google Patents
A kind of ultraviolet radiation preventing transparency high separation thin film and application thereof Download PDFInfo
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Abstract
A kind of ultraviolet radiation preventing transparency high separation thin film and application thereof, it includes base material, after improvement, base material is coated with the gas-barrier layer that at least one of which inorganic compound is formed, the gas-barrier layer that inorganic compound is formed is coated with at least one of which nitrogen-doped titanium dioxide layer, in described nitrogen-doped titanium dioxide layer, nitrogen content is 0.5～1%, and the gross thickness of nitrogen-doped titanium dioxide layer is 100～300nm.The present invention reaches more than 99% to the absorbance of UVA, and the absorbance of UVB is reached more than 99%, can effectively prevent and protect content not encroached on by ultraviolet；Coating is thin, and thin film flexible is good, is using in the course of processing not embrittlement, it is possible to keep high barrier, and film clarity is maintained at the transmitance to visible ray and reaches more than 80%, meet and pack visual requirement.Can be used for the fields such as food and medicine packaging, electron device package.
Description
Technical field
The present invention relates to a kind of high performance thin film, particularly to transparency high separation thin film and the application thereof of a kind of ultraviolet radiation preventing.
Background technology
Inorganic high-isolation film shows barrier height compared with multi-layer co-extruded Obstruct membrane, saves resource, advantages of environment protection, have compared with aluminium foil or metallized film simultaneously transparent visual, can the advantage such as microwave heating sterilizing, therefore it is widely used to fatty foods, the packaging of the sterilizing heating soft drink such as food and beverage, medicated beer, fruit juice, and is used for encapsulating electronic component.It is combined with PA and CPP again at PET one or two sides plating silicon oxide film as Application No. 201220280872.4 Chinese patent uses, makes the high-barrier composite membrane of resistance to steaming and decocting.
Transparent packaging film can intuitively observe content, gives aesthetic and direct feel, and market application constantly expands.But penetrating of ultraviolet cannot be prevented, if package goods is irradiated with for a long time, particularly in the megastore needing high light to decorate or to illuminate or supermarket, the food having added pigment will variable color, affect outward appearance, even cause nutritional labeling such as vitamin, protein, amino acid whose destruction.Electronic light emitting devices is owing to needing high-resistant diaphragm to encapsulate water vapor sensitive, but its light radiation launched the most increasingly causes concern, and under irradiating for a long time in life and work, easily eyes and skin to people damage.
Inorganic high-resistant diaphragm is relatively strong to the absorption of UVB (280～315nm), but poor to the assimilation effect of UVA (315～400nm).As silicon oxide high-resistant diaphragm can reach more than 99% to the assimilation effect of UVB, but poor to the assimilation effect of UVA.
TW200940341 coats the acrylate layer containing organic uv absorbers on base material, then is coated with thereon or coating inorganic oxide barrier layers.Organic uv absorbers in coat is poisonous, unstable, and growth over time can inner layer migrate, and affects food safety.
Another is to use ultrafine inorganic particle ultraviolet absorber nontoxic, stable, but in addition polymeric substrate, after film forming, nanoparticle does not cross-link with plastics macromolecular chain, exists with nano-particle, can affect the barrier properties for gases of thin film.
United States Patent (USP) US5156882 uses inorganic nano titanium oxide coating anti-ultraviolet, compared with adding ultraviolet absorber with adhesive, titanium oxide coating has strong absorption, stablizes the ultraviolet of 300-350nm, and thickness of coating is the biggest, and particle diameter is the biggest, ultraviolet absorption peak red shift, thickness 500-1000nm to be reached, has a strong absorption to the ultraviolet of 350-400nm, but thickness is the thickest easily makes polymeric film substrate embrittlement, titanium oxide coating and obstruct coating in use can be made easily to split, be substantially reduced barrier.
The Chinese patent of Publication No. CN1594646, on glass or the rigid substrate such as pottery and steel disc, uses sputtering method to prepare nitrogen-doped titanium dioxide layer film, and ultraviolet cutoff wavelength is more than 390nm, it is seen that light mean transmissivity is 70%～80%.Nitrogen element content in the film is 3～10%, can affect packaging external appearance with flavous color in the transparent color of thin film.
Summary of the invention
The technical problem to be solved in the present invention is the weak point existed for prior art, it is provided that a kind of ultraviolet radiation preventing transparency high separation thin film, it has the advantages that ultraviolet radiation preventing, high resistant water proof oxygen function and visible light permeability are good；It addition, the ultraviolet-absorbing of described thin film is strong, high to water oxygen barrier performance, and this thin film is without noxious substance interpolation, non-environmental-pollution, technique simplification, and cost reduces.
For solving above-mentioned technical problem, the present invention adopts the following technical scheme that
A kind of ultraviolet radiation preventing transparency high separation thin film, it includes base material, after improvement, base material is coated with the gas-barrier layer that at least one of which inorganic compound is formed, the gas-barrier layer that inorganic compound is formed is coated with at least one of which nitrogen-doped titanium dioxide layer, in described nitrogen-doped titanium dioxide layer, nitrogen content is 0.5～1%, and the gross thickness of nitrogen-doped titanium dioxide layer is 100～300nm.
In such scheme, the thickness of described nitrogen-doped titanium dioxide layer is 150～200nm.
In such scheme, being coated with at least one of which titanium dioxide layer between base material and gas-barrier layer, titanium dioxide layer gross thickness is 50～200nm.
In such scheme, titanium dioxide layer gross thickness is 100～150nm.
In such scheme, the visible light transmissivity of described ultraviolet radiation preventing transparency high separation thin film is more than 80%.
In such scheme, described ultraviolet radiation preventing transparency high separation thin film oxygen permeating amount is less than 0.5 ml m-2·d-1, permeable amount is less than 0.1g m-2·d-1。
In such scheme, described base material be visible light transmissivity be the flexible polymeric substrate of more than 85%.
In such scheme, described base material is the one in PET, PEN.
In such scheme, the gas-barrier layer that described inorganic compound is formed is the one in silicon or the oxide of aluminum, nitrogen oxides.
A kind of ultraviolet radiation preventing transparency high separation thin film, it is characterised in that described high-isolation film is for fields such as food and medicine packaging, electron device package.
Compared with prior art, there is advantages that
The present invention is coated with nitrogen-doped titanium dioxide layer on transparency high interlayer so that the absorbance of UVA is reached more than 99%, and the absorbance of UVB is reached more than 99%, can effectively prevent and protect content not encroached on by ultraviolet；When nitrogen-doped titanium dioxide layer is positioned at outermost layer simultaneously, having hydrophobic effect, contact angle is more than 95 °, prevents the surface adsorption of steam, delays the infiltration time of steam, improves water proofing property, makes oxygen permeating amount be less than 0.5 ml m-2·d-1, permeable amount is less than 0.1g m-2·d-1.Meanwhile, control the content of nitrogen so that it is transparency is maintained at the transmitance to visible ray and reaches more than 80%, meet and pack visual requirement.Nitrogen-doped titanium dioxide thickness of coating is 100～300 nanometers, and coating is thin, and thin film flexible is good, is using in the course of processing not embrittlement, it is possible to keep high barrier.
The anti-ultraviolet transparent high-isolation film of the present invention, the titanium oxide layer being coated with is between base material and high-obstruction, the N doping titanium oxide coating being coated with has Superhydrophilic, can form capillary tube thus adsorb the steam of infiltration between titanium oxide, and steam can be delayed further to penetrate in packaging again.
The high-obstruction that the inorganic compound that the vacuum deposition device of the present invention is coated with is formed is stronger to the absorption of UVB (280～315nm), titanium oxide coating has strong absorption to the ultraviolet of 300-370nm, nitrogen-doped titanium dioxide coating is strong absorption along with the ultraviolet under 400nm can be had by coating, and three kinds of coating membrane structures can effectively prevent penetrating of below 400nm ultraviolet.
Accompanying drawing explanation
Fig. 1 is the ultraviolet radiation preventing transparency high separation thin film schematic diagram of embodiment 1.
Fig. 2 is the ultraviolet radiation preventing transparency high separation thin film schematic diagram of embodiment 2.
Fig. 3 is the ultraviolet radiation preventing transparency high separation thin film schematic diagram of embodiment 3.
Fig. 4 is the ultraviolet radiation preventing transparency high separation thin film schematic diagram of embodiment 4.
Fig. 5 is the ultraviolet radiation preventing transparency high separation thin film schematic diagram of embodiment 5.
In figure: 1-base material；2-gas-barrier layer；3-nitrogen-doped titanium dioxide layer；4-titanium oxide layer；2a-the first gas-barrier layer；2b-the second gas-barrier layer；3a-the first nitrogen-doped titanium dioxide layer；3b-the first nitrogen-doped titanium dioxide layer；4a-the first titanium oxide layer；4b-the second titanium oxide layer.
Detailed description of the invention
Ultraviolet radiation preventing transparency high separation membrane structure
Ultraviolet radiation preventing transparency high separation membrane structure of the present invention is to be coated with the gas-barrier layer that at least one of which inorganic compound is formed on base material, is coated with at least one of which nitrogen-doped titanium dioxide layer on the gas-barrier layer that inorganic compound is formed.
The structure of another ultraviolet radiation preventing transparency high separation thin film of the present invention is to be coated with at least one of which titanium dioxide layer on base material, the gas-barrier layer that at least one of which inorganic compound is formed on titanium dioxide layer, is coated with at least one of which nitrogen-doped titanium dioxide layer on the gas-barrier layer that inorganic compound is formed.
The base structure of the present invention is base material/gas-barrier layer/nitrogen-doped titanium dioxide layer；
One preferred structure of the present invention is base material/titanium dioxide layer/gas-barrier layer/nitrogen-doped titanium dioxide layer；
Another kind preferred structure of the present invention is base material/titanium dioxide layer/gas-barrier layer/titanium dioxide layer/gas-barrier layer/nitrogen-doped titanium dioxide layer；
Another kind preferred structure of the present invention is to be provided with titanium dioxide layer/gas barrier layer unit that multilamellar repeats between base material and nitrogen-doped titanium dioxide layer.
Nitrogen-doped titanium dioxide layer
The nitrogen content 0.5 ~ 1% of the nitrogen-doped titanium dioxide layer of the present invention, further preferred content is 0.5～0.8%.Very little, the thickness of coating must strengthen and can be only achieved the effect effectively absorbing UV nitrogen content, but enlarged in thickness easily makes thin film become fragile, and is unfavorable for follow-up processed and applied, and hydrophobic effect weakens simultaneously, is unfavorable for the decline of barrier；Content is more than 1%, then gradually carry flavous color in the transparent color of high-barrier transparency film, it is seen that light transmission rate declines.
The nitrogen content lower limit of multifunctional light electronics energy disperse spectroscopy test nitrogen-doped titanium dioxide layer is 1%, the content nitrogen-doped titanium dioxide layer less than 1%, can according to other technological parameter identical under, monomer is more constant than each constituent content in identical obtained coating film with reaction gas flow, and regulation titaniferous monomer obtains with nitrogenous gas ratio;Computational methods are as follows:
Oxygen and flow of monomer are than constant for a, and monomer and nitrogenous reaction gas flow ratio is for b, and in reacting gas, the content of nitrogen element is 1/ (ab+b+1), on the basis of the nitrogen-doped titanium dioxide layer using content to be 1%；The monomer increased is b1 with the flow-rate ratio of nitrogenous gas, and in reacting gas, the content of nitrogen element becomes 1/ (ab1+b1+1), then in the nitrogen-doped titanium dioxide layer plated, nitrogen element c is:
In embodiment 1, in nitrogen-doped titanium dioxide layer, nitrogen content is 1%, uses the test of multifunctional light electronics energy disperse spectroscopy.
In embodiment 3, a=4, b1=11,
Then
Nitrogen-doped titanium dioxide layer of the present invention can use known mode to be formed, it is preferred to use vacuum coating equipment is coated with, such as chemical vapour deposition technique, sputtering method etc., more preferably using plasma chemical vapour deposition technique.The nitrogen-doped titanium dioxide layer of the present invention can be coated with formation by one or many, the gross thickness of nitrogen-doped titanium dioxide layer is 100～300nm, it is preferably 150～200nm, if nitrogen-doped titanium dioxide layer is the thickest, the easy embrittlement of coating, in use there is rupture of membranes, affect performance, meanwhile, cause high cost, uneconomical；If coating is the thinnest, then the effect of anti-ultraviolet is bad.
Nitrogen-doped titanium dioxide can make ultraviolet absorption peak red shift, can have strong absorption to the ultraviolet of below 400nm.N doping titanium oxide layer has hydrophobicity simultaneously, and contact angle is more than 95 °, prevents the surface adsorption of steam, delays the infiltration time of steam, water vapor rejection plays first barriering effect.
Nitrogen-doped titanium dioxide layer of the present invention, can be formed with the titanium dioxide layer of Multiple depositions different nitrogen contents, preferably outermost layer is the nitrogen-doped titanium dioxide layer that nitrogen element ratio is higher, to improve hydrophobic effect, internal layer is nitrogen element ratio less nitrogen-doped titanium dioxide layer, slow down the time entering gas-barrier layer of steam, improve the block-water performance of thin film further.
Titanium dioxide layer
The present invention is preferably coated with at least one of which titanium dioxide layer between base material and gas-barrier layer.Titanium dioxide layer can have shielding action to the ultraviolet of 300-370nm, and light resistance, weatherability, chemical stability, heat resistance are all fine, nontoxic, with low cost.The addition of titanium dioxide layer can suitably reduce the thickness of nitrogen-doped titanium dioxide layer, reduces the fragility of thin film.Titanium dioxide layer has hydrophilic simultaneously, can adsorb the steam of the barrier layer formed through inorganic compound, delays steam toward the infiltration of base material further, plays further assosting effect to intercepting steam.
Base material
Base material used by the present invention is general transparent polymeric support, material and thickness to base material are not particularly limited, light transmittance preferably reaches more than 80%, more preferably more than 85%, the flexible polymeric substrate of particularly preferred more than 90% such as polyester film, nylon membrane, polypropylene film, transparent fluororesin, polyamide, fluorination polyamide, polyimides, polyimide amide, polytrimethylene ether amide, epoxy resin, Merlon, polyurethane resin, polytrimethylene ether ethyl ketone ester, ester ring type polysulfones, polyether sulfone, polyacrylate, polytrimethylene ether, fluorenes ring degeneration Merlon, alicyclic ring degeneration Merlon, fluorenes ring degeneration polyester, cyclic olefine copolymer etc..The preferably one in polyethylene terephthalate (PET), PEN (PEN).Base material thickness is not particularly limited, preferably 10～250 μm, more preferably 12～200 μm.
Gas-barrier layer
The composition of gas-barrier layer of the present invention, for metal or nonmetal oxide, nitrogen oxides, oxycarbide, such as, can be selected from containing silicon, aluminum, stannum, zinc, titanium, magnesium, zirconium, nickel, cobalt, ferrum, lead, copper, palladium, the oxide of one or more metals, nitrogen oxides, oxycarbide, carbonitride, the carbon nitrogen oxide such as indium.Wherein, preferably silicon, aluminum, stannum, zinc, the metal-oxide of titanium, nitride and nitrogen oxides, more preferably silicon, the oxide of aluminum, nitrogen oxides, it is also possible to containing other auxiliary element.
The plating method of gas-barrier layer uses vacuum coating equipment, suitably selects according to selected barrier layer constituent kind.Preferably employ chemical vapour deposition technique, sputtering method, ion vapour deposition method etc..In terms of the tack of thin film, barrier, it is preferred to use plasma chemical vapor deposition.The thickness of gas-barrier layer is generally 10～500nm, and more preferably 50～150nm, it is ensured that thin film has enough barriers, does not occur embrittlement good with the tack of base material simultaneously.
Individually gas-barrier layer can reach more than 99% to the absorption of UVB, and the ultraviolet ray transmissivity for UVA, 320nm wavelength is 40%, the ultraviolet ray transmissivity about 80% of 400nm wavelength, and between 320nm ~ 400nm, the transmitance of wavelength is between 40 ~ 80%.
By using above-mentioned base material, gas-barrier layer, nitrogen-doped titanium dioxide layer, and control the thickness of each layer, the light transmittance of the ultraviolet radiation preventing transparency high separation thin film obtaining the present invention be visible light transmissivity be more than 80%, oxygen permeating amount is less than 0.5 ml m-2·d-1, permeable amount is less than 0.1g m-2·d-1, the transmitance of UVA and UVB is more than 99%, it is possible to for fields such as food and medicine packaging, electron device package, visual requirement can be met, the requirement of permeable oxygen flow can be met again.
The gas-barrier layer that the inorganic compound that vacuum deposition device of the present invention is coated with is formed is stronger to the absorption of UVB (280 ~ 315nm), nitrogen-doped titanium dioxide coating is strong absorption along with the ultraviolet of below wavelength 400nm can be had by coating, and two kinds of coating films are coated with and can effectively prevent penetrating of the following ultraviolet of wavelength 400nm；Titanium oxide coating has strong absorption to the ultraviolet of wavelength 300-370nm, ultraviolet radiation preventing that three kinds of coating films are coated with transparent prevent the following ultraviolet of wavelength 400nm to penetrate aspect performance the most excellent, it is prevented from penetrating of all-wave ultraviolet, there is again high resistant water proof oxygen performance simultaneously.This thin film can be used for the fields such as food and medicine packaging, electron device package.Ultraviolet radiation preventing high-barrier transparency film is applied to food and medicine packaging, due to the oxygen performance that blocks water that it is outstanding, can be greatly prolonged the shelf-life of packing material, excellent UV resistance performance can prevent the loss of the compositions such as pigment in content, protein, aminoacid, also ensure that the transparency of packaging simultaneously.Being applied to electron device package, can prevent internal components from being affected by water oxygen, the most also can intercept the ultraviolet radiation that electronic light emitting devices is launched, the eyes of protection people and skin are from ultraviolet light harms.
Preparation method
As a example by plasma gas-phase deposit (PECVD):
1. choose the transparency base material more than 85%；
2. it is coated with gas-barrier layer by PECVD mode, concrete steps:
1. cleaning base material or titanium dioxide layer with the argon plasma that air pressure is 10Pa, scavenging period is 2min；
It is passed through argon, monomer, nitrous oxide gas or oxygen the most successively in vacuum chamber；
3. carrying out chemical vapour deposition reaction under the pulse power excites, deposition prepares gas-barrier layer.
3. prepare nitrogen-doped titanium dioxide layer by PECVD mode, comprise the following steps:
1. air pressure is the argon plasma purge gas barrier layer of 10Pa, and scavenging period is 2min；
It is passed through argon, monomer (isopropyl titanate Ti (IPO the most successively in vacuum chamber4)), nitrous oxide gas and oxygen；
3. carrying out chemical vapour deposition reaction under the pulse power excites, deposition prepares nitrogen-doped titanium dioxide layer.
4. prepare titanium dioxide layer by PECVD mode
1. cleaning base material with the argon plasma that air pressure is 10Pa, scavenging period is 2min；
It is passed through argon, monomer (isopropyl titanate Ti (IPO the most successively in vacuum chamber4)) and oxygen；
3. carrying out chemical vapour deposition reaction under the pulse power excites, deposition prepares two sample titanium layers.
UV resistance high-barrier transparency film can be combined into ultraviolet radiation preventing high-isolating packaging film with PA, CPP film by dry compound machine.
Below by specific embodiment, the present invention is described in further detail.
Embodiment 1
By plasma enhanced chemical vapor deposition method upper one layer of thick for the plating 100nm silicon oxide layer (2) of the PET base material (1) that 12 μ m-thick, light transmittance are 91%；Technological parameter is:
| Pulse power power | 30w | |
| Oxygen and monomer ratio | O2:HMDSO | 2:1 |
| Dutycycle | 15% | |
| Operating pressure | 10Pa |
By plasma enhanced chemical vapor deposition method (PECVD) at N doping titanium oxide layer (3) that nitrogen content is 1% thick for silicon oxide layer (2) upper plating 200nm, technological parameter is:
| Radio-frequency power supply power | 30w | |
| Monomer and nitrous oxide flow ratio | Ti(IPO4) :N2O | 8:1 |
| Oxygen and flow of monomer ratio | O2:Ti(IPO4) | 4:1 |
| Operating pressure | 65Pa |
Concrete structure is as shown in Figure 1.
Embodiment 2
By plasma enhanced chemical vapor deposition method at the technological parameter of titanium oxide layer (4) thick for the PEN base material (1) that 12 μ m-thick, light transmittance are 87% upper plating plating 120nm it is:
| Radio-frequency power supply power | 20w | |
| Oxygen and flow of monomer ratio | O2:Ti(IPO4) | 3:1 |
| Operating pressure | 65Pa |
Using ion vapour deposition method or the alumina layer (2) of sputtering method plating 100nm thickness on titanium oxide layer (4) layer, be coated with thick N doping titanium oxide layer (3) that nitrogen content is 1% of 150nm on alumina layer (2), technological parameter is with embodiment 1.Concrete structure is as shown in Figure 2.
Embodiment 3
By plasma enhanced chemical vapor deposition method (PECVD) at upper the first titanium oxide layer (4a) thick for plating 50nm of the PET base material (1) that 100 μ m-thick, light transmittance are 89%；First titanium oxide layer (4a) layer plates 100nm thickness silicon oxynitride and forms the first gas-barrier layer (2a)；First gas-barrier layer (2a) is coated with thick the second titanium oxide layer (4b) of 100nm；Second titanium oxide layer (4b) is coated with the second gas-barrier layer (2b) that silicon oxide layer thick for 50nm is formed, the N doping titanium oxide layer of 100nm thickness nitrogen content 0.7% it is coated with again on the second gas-barrier layer (2b), according to other technological parameter identical under, monomer and reaction gas flow are than the constant principle of each constituent content in identical prepared coating film, regulation monomer is 11:1 with nitrous oxide flow ratio, and other technological parameter is with embodiment 1.Silicon oxynitride layer is coated with in reacting gas addition nitrous oxide gas, and the process for plating parameter of other technological parameter and silicon oxide layer is with embodiment 1.The technological parameter of titanium oxide layer is with embodiment 2.Concrete structure is as shown in Figure 3.
Embodiment 4
By plasma enhanced chemical vapor deposition method at the upper titanium oxide layer (4) thick for plating 200nm of the PET base material (1) that 12 μ m-thick, light transmittance are 91%, technological parameter is with embodiment 2；Titanium oxide layer (4) layer plates the thick silicon oxide layer (2) of 100nm；Plating thick N doping titanium oxide layer (3) that nitrogen content is 1% of 100nm on silicon oxide layer, technological parameter is with embodiment 1.
Embodiment 5
By plasma enhanced chemical vapor deposition method in the PET base material (1) plating 50nm thickness titanium oxide layer (4) that 12 μ m-thick, light transmittance are 91%, technological parameter is with embodiment 2.Titanium oxide layer (4) layer plates the thick silicon oxide layer (2) of 50nm, silicon oxide layer is coated with the first nitrogen-doped titanium dioxide layer (3a) that the N doping titanium oxide of 200nm thickness nitrogen content 0.5% is formed, according to other technological parameter identical under, monomer and reaction gas flow are than the constant principle of each constituent content in identical prepared coating film, regulation monomer is 15:1 with nitrous oxide flow ratio, the second nitrogen-doped titanium dioxide layer (3b) that the N doping titanium oxide of nitrogen content 1% thick for plating 100nm the most thereon is formed, the technological parameter of each coating is with embodiment 1.
Comparative example 1
By plasma enhanced chemical vapor deposition method at the silicon dioxide layer (2) thick for PET base material (1) upper plating 100nm that 12 thick μ m-thick, light transmittance are 91%, the technological parameter of coating is with embodiment 1.
Comparative example 2
By plasma enhanced chemical vapor deposition method at the silicon oxide layer (2) thick for PET base material (1) upper plating 100nm that 12 thick μ m-thick, light transmittance are 91%, N doping titanium oxide layer (3) that nitrogen content is 2% thick for (2) plating 100nm on silicon oxide layer, other technological parameter of each coating is with embodiment 1.
Comparative example 3
By plasma enhanced chemical vapor deposition method at the silicon oxide layer (2) thick for PET base material (1) upper plating 100nm that 12 thick μ m-thick, light transmittance are 91%, N doping titanium oxide layer (3) that nitrogen content is 1% thick for (2) plating 500nm on silicon oxide layer, the technological parameter of each coating is with embodiment 1.
Embodiment and comparative example structure composition are listed in table 1, and the thin film as obtained by its method carries out uv absorption, light transmittance, permeability rate, oxygen transmission rate evaluation, and experimental result is listed in table 2.
Performance detects:
(1) uv-vis spectra test: use Hitachi's U-3000 ultraviolet spectrophotometer.
(2) elemental composition analysis: the Kratos Axis that Japan SHIMADZ produces
Ultra multifunctional light electronics energy disperse spectroscopy.
(3) light transmittance: use haze meter (DIFFUSION company of Britain M57D) to carry out testing total light transmittance.
(4) oxygen permeability test: the 8001 oxygen flow instrument that American I llinuois produces, test condition is 23 DEG C, 80% humidity.
(5) water permeability test: AQUATRAN 1 permeability tester that MOCON company of the U.S. produces, test condition is 37.8 DEG C, 90% humidity.
Table 1:
Note: in table, according to band * numerical value, other technological parameter is identical, monomer is more constant than each constituent content in identical obtained coating film with reaction gas flow, calculates gained reduced value by regulation monomer with nitrous oxide flow ratio.
Table 2:
The uv absorption maximum wavelength of anti-ultraviolet transparent high-isolation film obtained by embodiment 1-5 is more than 400nm; can prevent all-wave ultraviolet (UVA and UVB) from radiating; can effectively prevent and protect content not encroached on by ultraviolet; ensure that the transmitance of visible ray reaches more than 80% simultaneously, the visual requirement of packaging can be met；Having water oxygen high barrier, oxygen permeating amount is less than 0.5 ml m-2·d-1, permeable amount is less than 0.1g m-2·d-1, it is greatly prolonged the package goods life-span.
Comparative example 1 is only to be coated with gas-barrier layer on base material, does not add N doping titanium oxide or titanium oxide UV resistance layer, and the obstruct to ultraviolet can only achieve 310nm, it is impossible to effectively prevents UVA(315-400nm) irradiation of ultraviolet.Comparative example 2 compares with embodiment 1, and in N doping titanium oxide layer, the content of nitrogen strengthens, and carries flavous color, affects outward appearance, and visible light transmissivity drops to less than 80% in the transparent color of high-barrier transparency film.Comparative example 3 compares with embodiment 1, strengthen N doping titanium oxide layer thickness to 500nm, thickness of coating increases, and coating pin hole adds up, and forms crack, the oxygen performance that blocks water of thin film can be affected, also can reduce visible light transmissivity simultaneously, and during following process, the easy embrittlement of thin film, cause coating to rupture, affect UV resistance and the oxygen performance that blocks water.
Claims (9)
1. a ultraviolet radiation preventing transparency high separation thin film, it includes base material, base material is coated with the gas-barrier layer that at least one of which inorganic compound is formed, at least one of which titanium dioxide layer it is coated with between base material and gas-barrier layer, it is characterized in that, titanium dioxide layer gross thickness is 50-200nm, the gas-barrier layer that inorganic compound is formed is coated with at least one of which nitrogen-doped titanium dioxide layer, in described nitrogen-doped titanium dioxide layer, nitrogen content is 0.5-1%, and the gross thickness of nitrogen-doped titanium dioxide layer is 100-300nm.
Ultraviolet radiation preventing transparency high separation thin film the most according to claim 1, it is characterised in that the gross thickness of described nitrogen-doped titanium dioxide layer is 150-200nm.
Ultraviolet radiation preventing transparency high separation thin film the most according to claim 1, it is characterised in that titanium dioxide layer gross thickness is 100-150nm.
Ultraviolet radiation preventing transparency high separation thin film the most according to claim 1, it is characterised in that the visible light transmissivity of described ultraviolet radiation preventing transparency high separation thin film is more than 80%.
Ultraviolet radiation preventing transparency high separation thin film the most according to claim 4, it is characterised in that described ultraviolet radiation preventing transparency high separation thin film oxygen permeating amount is less than 0.5ml m-2·d-1, permeable amount is less than 0.1g m-2·d-1。
Ultraviolet radiation preventing transparency high separation thin film the most according to claim 5, it is characterised in that described base material be visible light transmissivity be the flexible polymeric substrate of more than 85%.
Ultraviolet radiation preventing transparency high separation thin film the most according to claim 6, it is characterised in that described base material is the one in PET, PEN.
Ultraviolet radiation preventing transparency high separation thin film the most according to claim 7, it is characterised in that the gas-barrier layer that described inorganic compound is formed is the one in silicon or the oxide of aluminum, nitrogen oxides.
9. the ultraviolet radiation preventing transparency high separation thin film as according to any one of claim 1-8, it is characterised in that described high-isolation film is used for food and medicine packaging, electron device package.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02266927A (en) * | 1989-04-10 | 1990-10-31 | Toppan Printing Co Ltd | Preparation of titanium oxide deposited film |
| CN1594646A (en) * | 2004-06-30 | 2005-03-16 | 武汉理工大学 | Hydrophobic and ultraviolet radiation proof transparent film and preparation thereof |
| JP2007083493A (en) * | 2005-09-21 | 2007-04-05 | Fujifilm Corp | Gas-barrier film and organic device using the film |
| CN102762366A (en) * | 2009-12-24 | 2012-10-31 | 东洋纺织株式会社 | Gas barrier multilayer film |
| CN103194731A (en) * | 2013-04-12 | 2013-07-10 | 中国科学院山西煤炭化学研究所 | Method for preparing nitrogen-doped titanium dioxide porous membrane |
| CN103382549A (en) * | 2013-07-27 | 2013-11-06 | 中国乐凯集团有限公司 | Production method for multilayered structural high barrier film |
| CN103764387A (en) * | 2011-09-07 | 2014-04-30 | 东丽株式会社 | Gas barrier film |
Family Cites Families (1)
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| KR101793047B1 (en) * | 2010-08-03 | 2017-11-03 | 삼성디스플레이 주식회사 | flexible display and Method for manufacturing the same |
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2014
- 2014-05-29 CN CN201410233985.2A patent/CN104175663B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02266927A (en) * | 1989-04-10 | 1990-10-31 | Toppan Printing Co Ltd | Preparation of titanium oxide deposited film |
| CN1594646A (en) * | 2004-06-30 | 2005-03-16 | 武汉理工大学 | Hydrophobic and ultraviolet radiation proof transparent film and preparation thereof |
| JP2007083493A (en) * | 2005-09-21 | 2007-04-05 | Fujifilm Corp | Gas-barrier film and organic device using the film |
| CN102762366A (en) * | 2009-12-24 | 2012-10-31 | 东洋纺织株式会社 | Gas barrier multilayer film |
| CN103764387A (en) * | 2011-09-07 | 2014-04-30 | 东丽株式会社 | Gas barrier film |
| CN103194731A (en) * | 2013-04-12 | 2013-07-10 | 中国科学院山西煤炭化学研究所 | Method for preparing nitrogen-doped titanium dioxide porous membrane |
| CN103382549A (en) * | 2013-07-27 | 2013-11-06 | 中国乐凯集团有限公司 | Production method for multilayered structural high barrier film |
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