Background technology
As everyone knows, Trend of High Obstructive Materials Ordnance Engineering College generally refers to high oxygen barrier material to food composite membrane, as nylon membrane (PA), ethylene/vinyl alcohol copolymer (EV-OH), but for Key works Drug packing, medicine is a kind of high added value, the specialty goods that security reliability requirement is high, most medicine is responsive to steam, and easy moisture absorption is made moist and loses drug effect; More there are some special medicines, its active ingredient is to oxygen sensitive, very easily oxidized and lose drug effect, thus in order to ensure the safety and effectiveness of medicine in shelf life, extend its shelf-life simultaneously, this just requires that drug packing material must have higher barrier property, especially for oxygen and steam.At present in high-barrier drug packing material, mainly contain following several: pure aluminum foil composite, vacuum plated aluminum film, sandwich construction composite membrane, PVDC (polyvinylidene chloride) coat film, plasma activated chemical vapour deposition SiOx film.
Except the packaging of the prepared slices of Chinese crude drugs and low-grade electuary, pharmaceutical packaging composite membrane is substantially based on pure aluminum foil composite, but aluminium foil is a kind of special material being different from plastics, the problems such as the aluminium foil layer in foil laminated film is worn in packaging, transport, pressure in sales process, break, jackknifing, high barrier aluminium foil layer can be caused to be destroyed, although can not gas leakage be produced, but its barrier property is just made a discount greatly, have a strong impact on the shelf-life of product, and this composite membrane can consume a large amount of metallic aluminum materials, and being recycled of discarded aluminium foil is also more difficult.
Vacuum plated aluminum film be under high vacuum state by aluminum evaporation on various basement membrane, its aluminium coated is thin.This film is except the characteristic with plastic-based film, also there is ornamental and good barrier, especially various plastic basis material is after aluminizing, light transmittance, oxygen transmission rate (OTR) and moisture-vapor transmission (WVTR) reduce by tens times or hundreds of times,) reduce by tens times or hundreds of times
Sandwich construction medical package film generally adopts PE/ bonding agent/PA/ bonding agent/PE/ binding agent/PA/ bonding agent/PE9 Rotating fields, and also can replace PA with PP (polypropylene), other structures are the same, and thickness is generally 0.05 ~ 0.4mm.The number of plies of current coextruded film is in continuous increase, and existing many companies can produce 8 layers, 9 layers even the medical package film of 11 layers.Bonding agent/PE9 Rotating fields, also can replace PA with PP (polypropylene), other structures are the same, and thickness is generally the production line of 0.05 ~ class composite membrane mainly from external import, and this just considerably increases the cost of manufacture of Key works Drug packing.
PVDC composite coating film obtains extensive use in Key works Drug packing, can play resistance and wet, protects the effect such as taste, protection against the tide.Current PVDC is on the market actually the copolymer of vinylidene chloride (VDC) and vinyl chloride or acrylic monomers, and content of monomer is generally 75% ~ 90%.In high-barrier medical packaging, it uses usually used as coating material, PP, PE, CPP, PET film are coated with the laminated film of 2 ~ 4 μm of PVDC, its gas permeability can be made, poisture-penetrability is best suited for the blister package film and combined package bag such as packaging particulate material, powder etc. that manufacture medicine.
Compared with other packaging material, the materials with high barrier property of PVDC is leading.Experiment shows, in 24 hours, temperature is 30.8 DEG C, relative humidity is under the condition of 90%, and the WVTR on every square metre of PVDC area is only 0.8 to 4.7 gram, and PA film is 372 to 430 grams, and PE film is 18.6 grams; In 24 hours, temperature is 20.3 DEG C, relative humidity is under the condition of 60%, and thickness is the PVDC of 24.7 microns, and its OTR is only 1.2 to 26.7 milliliters, and PA film is 40.3 milliliters, and PE film is 3875 to 8000 milliliters.In the U.S., PVDC goods are confirmed as the plastic material of non-toxic and safe, can be used for packaging for foodstuff; In Germany, PVDC packaging material are described as environmentally friendly packing material, have " green " mark; Prepacked food, medicine, chemical products etc. that Japan, Korea S circulate in the market, have about 60% to adopt PVDC goods to pack.PVDC, since appearance, just with the choke moisture resistance of its excellence, grease resistance, every flavour property, low temperature heat seal etc., in the current multicoloured plastics package world, has become a kind of packaging material that materials with high barrier property is best.
PVDC is high-tech new product, and with high content of technology, difficulty is large, no matter be polymerization technique, or plastic processing, all need very large input.The domestic PVDC for acceptable packaging material production is all by external import at present, and these products all obtain the accreditation of U.S. FDA (FDA (Food and Drug Adminstration)), may be used for the packaging of medicine and food.Domestic existing manufacturer production PVDC emulsion, but quality still has larger gap compared with import, is mainly manifested in the aspects such as barrier, coating homogeneity, stability, wholesomeness.The barrier property of PVDC product is no doubt very outstanding, but its production technology is monopolized, and China can only rely on import, so its cost is very high, fails at home to be used on a large scale.
In sum, in the urgent need to developing a new product, make it can reach high obstructing performance required for Key works Drug packing, can also accomplish that production technology is simple, cost of manufacture is low, therefore carry out surface modification to present widely used PE film, the method utilizing plasma and the method utilizing ald are at the organic SiO of its surface deposition
xnano coating and inorganic Al
2o
3nano coating be can yet be regarded as a kind of effective method, because PE film production process is simple, cost is low, the also very low and environmental protection of modification cost, in addition typical medicine widely uses in packing at home at present, there is good application space, market, so modifiedly a kind of effective high-barrier Key works Drug packing film should be able to be become to it
Utility model content
In order to overcome above-mentioned the deficiencies in the prior art, the utility model provides the Key works Drug packing high-barrier plastic film that a kind of surface is coated with MULTILAYER COMPOSITE nano coating, and this film is PE film, organic SiOx nano coating of 2-5 layer, the inorganic Al of layer 2-4 of 50-150 micron by thickness
2o
3nano coating forms.This film can improve the barrier properties to oxygen and steam greatly, can be applied to Key works Drug packing, and manufacture craft is simple, with low cost.
The technical scheme that the utility model adopts is:
Surface is coated with the Key works Drug packing high-barrier plastic film of MULTILAYER COMPOSITE nano coating, and there is organic nano SiO on its surface at PE film (1) successively alternating deposit
xcoating (2) and inorganic nano Al
2o
3coating (3), wherein the superiors are necessary for organic nano SiO
xcoating (2); Organic nano SiO
xcoating (2) is 2-5 layer, inorganic nano Al
2o
3coating (3) is 1-4 layer.
The thickness of described PE film (1) is 50-150 micron.
Every layer of organic nano SiO
xthe thickness of coating (2) is 30-50 nanometer, every layer of inorganic nano Al
2o
3the thickness of coating (3) is 5-15 nanometer.
So that widely used PE film is as packaging material in the market, its thickness is 50-150 micron, under certain vacuum degree, first utilizes oxygen gas plasma to carry out discharge process to its surface, increase its surface energy, and object improves follow-up SiO
xthe adhesive force of nano coating; And then utilize plasma enhanced chemical vapor deposition technology to deposit organic SiO of one deck 30-50 nano thickness at PE film surface
xcoating, finally utilizes technique for atomic layer deposition to deposit the inorganic Al of one deck 5-15 nano thickness again
2o
3nano coating.Organic SiO
xcoating and inorganic Al
2o
3nano coating is alternately stacked in PE film surface, and the two the number of plies can change the barriering effect of film to oxygen and steam.
Compared with prior art, the beneficial effects of the utility model are: owing to depositing organic SiO
xbefore nano coating, oxygen gas plasma process is carried out to PE film surface, added the surface energy of PE film surface, be conducive to organic SiO
xthe deposition of nano coating, can improve organic SiO greatly
xthe adhesive force of nano coating; Deposit organic SiO
xthe effect of nano coating is in order to inorganic Al
2o
3the deposition of nano coating and attachment, although organic SiO
xnano coating also has certain barrier property when certain thickness, but is far from inorganic Al
2o
3the barriering effect of nano coating is good, but inorganic Al
2o
3nano coating and the non-constant of organic PE adhesion of thin film, cause it not easily to deposit, very easily come off.And organic SiO
xthe structure of nano coating is organic principle structure and inorganic constituents structure, and organic principle structure better can make itself and the attachment of PE film surface, and inorganic constituents structure better can make itself and inorganic Al
2o
3nano coating better adheres to.So adopt this organic SiO on PE film
xnano coating and inorganic Al
2o
3the alternatively layered structure of nano coating, can improve the blocking effect of PE film to oxygen and steam greatly.
Detailed description of the invention:
Choose PE film as substrate film, thickness is 50-150 micron, can determine according to the packing instructions of Different Package thing; Before PE film surface depositing nano coating, first by the 95% alcohol immersion ultrasonic cleaning 3 minutes of PE film, then nitrogen dries up and puts into coating chamber immediately, be evacuated to 1.0Pa, pass into oxygen and carry out electric discharge 3 minutes, utilize the oxygen plasma produced to bombard PE film surface, to improve the surface energy of PE film surface, be conducive to follow-up Nano-meter SiO_2
xthe deposition of coating.After oxygen plasma bombardment, pass into the deposition that organic silicon monomer carries out nano oxidized silicon coating, deposit thickness is 30-50 nanometer; Then the method for ald is utilized, then at Nano-meter SiO_2
xthe surface deposition inorganic nano aluminum oxide film of coating, deposit thickness is 5-15 nanometer; Finally deposit one deck Nano-meter SiO_2 again
xcoating is as the sealer of inorganic oxide aluminium film, and this is a complete organic and inorganic-organic composite coating.Can by the OTR oxygen transmission rate of PE film by original 3000ml/m
2/ day drops to 30ml/m
2/ day, moisture-vapor transmission can by original 20g/m
2/ day drops to 5g/m
2/ day.In order to obtain better barriering effect, multilayer organic and inorganic-organic composite coating can be prepared, by organic nano SiO
xcoating and inorganic nano Al
2o
3the number of plies of coating increases, preferred organic Nano-meter SiO_2
xthe number of plies of coating is 2-5 layer, inorganic nano Al
2o
3the number of plies of coating is 1-4 layer.
Below in conjunction with accompanying drawing, the utility model is further illustrated.
As shown in Figure 1, high-barrier Key works Drug packing with PE film by PE film 1, organic nano SiO
xcoating 2 and inorganic nano Al
2o
3coating 3 forms, organic nano SiO
xcoating 2 is deposited directly to PE film 1 surface, inorganic nano Al
2o
3coating 3 is deposited on organic nano SiO
xthe surface of coating 2, in order to obtain better barriering effect, can increase organic nano SiO
xcoating 2, inorganic nano Al
2o
3the number of plies of coating 3, organic nano SiO
xcoating 2 must be positioned at the outermost of whole product.