CN103434250A - Preparation method of environmentally-friendly halogen-free cold-stamping molded composite aluminum foil material - Google Patents
Preparation method of environmentally-friendly halogen-free cold-stamping molded composite aluminum foil material Download PDFInfo
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- 229910052782 aluminium Inorganic materials 0.000 title abstract description 14
- 239000011888 foil Substances 0.000 title abstract description 14
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- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims abstract description 13
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- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims abstract description 8
- 239000000853 adhesive Substances 0.000 claims abstract description 8
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- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 claims abstract description 8
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- 239000005030 aluminium foil Substances 0.000 claims description 106
- 150000001875 compounds Chemical class 0.000 claims description 37
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 33
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 238000012545 processing Methods 0.000 claims description 22
- 229910052736 halogen Inorganic materials 0.000 claims description 21
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- 239000003795 chemical substances by application Substances 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
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- 238000007739 conversion coating Methods 0.000 claims description 8
- NMGYKLMMQCTUGI-UHFFFAOYSA-J diazanium;titanium(4+);hexafluoride Chemical compound [NH4+].[NH4+].[F-].[F-].[F-].[F-].[F-].[F-].[Ti+4] NMGYKLMMQCTUGI-UHFFFAOYSA-J 0.000 claims description 8
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- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 7
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- 239000004698 Polyethylene Substances 0.000 claims description 6
- DYAHQFWOVKZOOW-UHFFFAOYSA-N Sarin Chemical compound CC(C)OP(C)(F)=O DYAHQFWOVKZOOW-UHFFFAOYSA-N 0.000 claims description 6
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Abstract
The invention discloses a preparation method of an environmentally-friendly halogen-free cold-stamping molded composite aluminum foil material. A technical scheme adopted in the invention is characterized in that the method comprises the following steps: 1, chemical conversion treatment of an aluminum foil: carrying out chemical treatment of the aluminum foil through adopting a tannic acid treatment process, a phytic acid coating and silane coupling agent promotion method or an organosilane process to form a conversion layer on the aluminum foil; 2, uniformly coating the conversion layer of the aluminum foil with a heat sealing layer material by adopting a hot pressing technology; 3, uniformly coating the aluminum foil surface of a composite material prepared in step 2 with a special adhesive for polyurethane aluminum foil, and compounding with a nylon layer after a solvent volatilizes to prepare a composite aluminum foil material; and 4, carrying out heat treatment of the prepared composite aluminum foil material in a 60-80DEG C drying room for 12-24h, cutting, examining and warehousing. The composite aluminum foil material prepared in the invention has the advantages of halogen-free nontoxic components, good barrier property and long shelf life, and is very suitable for solid medicinal packaging because of its comprehensive properties.
Description
Technical field
The present invention relates to a kind of preparation method of medicinal aluminum foil material, be specifically related to the preparation method that a kind of environment friendly non-halogen can cold stamping shaped compound aluminium foil material, for solving existing medicinal aluminum foil, have the harm of halogen because containing the PVC material.
Background technology
In the solid drug package of existing market, the market share that the blister package occupation ratio that PVC and PTP aluminum foil material form is larger.The capsule of this material packing, tablet etc., for the user provides quantitative package, take conveniently, after taking out required medicine unit, and do not affect the preservation with other medicine unit of packing.But, there is the deficiency of two aspects in the PVC material: one, PVC itself contains halogen, some additives have also been added in process, impact due to heat sealed package, the factor such as storage temperature is too high, standing time is long, PVC can discharge halogen and other pernicious gas, may cause harmful effect to property of drug and personal safety; Two, the PVC material is on duty mutually to the barrier of water, oxygen, also is unfavorable for the long preservation of medicine.
For solving the poor problem of solid medicinal packing barrier, domestic several enterprise developments cold stamping shaped compound aluminium foil material, adopted the materials such as PVC, aluminium foil, nylon, polyester to be made into compound aluminium foil material, solved the problem of packing barrier property deficiency, but inner layer material still adopts the PVC material, the still harm of unresolved halogen and PVC additive.
The present invention has used for reference the cold stamping shaped aluminium foil structure occurred in the market, developed Halogen can be cold stamping shaped the solid medicinal compound aluminium foil material, improved the barrier of packing, be also compound aluminium foil material prepared by a kind of environment-friendly materials that adopt Halogen fully simultaneously.
Summary of the invention
The technical problem that the present invention solves has been to provide the preparation method that a kind of environment friendly non-halogen can cold stamping shaped compound aluminium foil material, and this preparation method adopts nontoxic chemical transforming process, adopts the environment-friendly materials of Halogen to be prepared fully.
Technical scheme of the present invention is: the preparation method that a kind of environment friendly non-halogen can cold stamping shaped compound aluminium foil material, it is characterized in that comprising the following steps: (1) aluminium foil chemical conversion is processed, and adopts tannic acid facture, phytic acid coating with silane coupler promotion law or organosilan method, aluminium foil to be carried out to chemical treatment and form conversion coating on aluminium foil layer; (2) adopt heat pressing process the hot sealing layer material to be coated on equably on the conversion coating of aluminium foil; (3) aluminium foil surface of the composite prepared by step (2) is coated with polyurethane aluminium foil adhesive specially equably, after solvent evaporates, with nylon layer, carries out the compound compound aluminium foil material that makes; (4) compound aluminium foil material made is put into to 60-80 ℃ of baking room and heat-treated 12-24h, cut, check, put in storage, wherein nylon layer adopts and extends nylon, aluminium foil layer adopts O type aluminium foil, hot sealing layer adopts one or more in modified poly ethylene, modified polypropene or thermoplastic elastomer (TPE), and described thermoplastic elastomer (TPE) is thermoplastic polyurethane, sarin resin, polyethylene enhancing sarin resin, POE, SBC, TPV or thermoplastic polyester elastomer block copolymer Hytrel.
In aluminium foil chemical conversion processing procedure of the present invention, the detailed process of tannic acid facture is: the chemical converting agent that is equipped with following concentration: tannic acid 8.2g/L, phosphoric acid 0.04g/L, F
-0.4g/L, Ti salt 0.05g/L, regulate and keep pH value=4.9 with NaOH, at first clean the aluminium foil surface greasy dirt with ethyl acetate, then at conversion temperature 30-60 ℃, under the condition of spray time 5-50 second, aluminium foil is carried out to the chemical conversion processing, and use 120 ℃ of hot air circulation wind of online drying plant to dry.
In aluminium foil chemical conversion processing procedure of the present invention, the phytic acid coating with the detailed process of silane coupler promotion law is: the chemical converting agent that is equipped with following concentration: ammonium titanium fluoride 10g/L, phytic acid 16g/L, silica gel 30g/L, the PVA(degree of polymerization 1400) 50g/L, regulate and keep pH value=5.3 with NaOH, at first clean the aluminium foil surface greasy dirt with ethyl acetate, then use spreader with 10mg/m
2coating weight aluminium foil is carried out to the chemical conversion processing, and use 120 ℃ of hot air circulation wind of online drying plant to dry, the collocation method wiring solution-forming that silane coupler is provided by manufacturer, be coated on the one side of aluminium foil conversion coating with plasma method, again dry.
In aluminium foil chemical conversion processing procedure of the present invention, the detailed process of organosilan method is: the chemical converting agent that is equipped with following concentration: ammonium titanium fluoride 10g/L, phytic acid 16g/L, silica gel 30g/L, the PVA(degree of polymerization 1400) 50g/L, regulate and keep pH value=5.3 with NaOH, at first clean the aluminium foil surface greasy dirt with ethyl acetate, then use spreader with 10mg/m
2coating weight aluminium foil is carried out to the chemical conversion processing, and use 120 ℃ of hot air circulation wind of online drying plant to dry.
Compound aluminium foil material prepared by the present invention; adopt nontoxic chemical transforming process; adopt the material of Halogen to be prepared fully; to the good barrier property of steam, oxygen, various gas, solvent, light tight line, and can be cold stamping shaped; both to medicine, provided safe preservation environment; being without fear of an attack from the rear during the protection customer consumption, having extended again the shelf life of medicine, is the ideal substitute that substitutes conventional P VC packaging material.
The accompanying drawing explanation
Fig. 1 is the structural representation of compound aluminium foil material of the present invention.
Drawing explanation: 1, nylon layer, 2, adhesive layer, 3, aluminium foil layer, 4, conversion coating, 5, hot sealing layer.
The specific embodiment
Further describe content of the present invention below in conjunction with drawings and Examples, but they do not do any restriction to the present invention.
Embodiment 1
A kind of environment friendly non-halogen can be cold stamping shaped compound aluminium foil material, structure and thickness from outside to inside are followed successively by: 25 μ m nylon layer 1,3 μ m adhesive layer 2,50 μ m aluminium foil layer 3,3 μ m conversion coatings 4 and 15 μ m added the modified poly ethylene hot sealing layer 5 of tackifier.By following processing step and technological parameter, prepare: (1) aluminium foil chemical conversion is processed: the chemical converting agent that is equipped with following concentration: tannic acid 8.2g/L, phosphoric acid 0.04g/L, F
-0.4g/L, Ti salt 0.05g/L, regulate and keep pH value=4.9 with NaOH, at first with ethyl acetate, clean the aluminium foil surface greasy dirt, and then conversion temperature 30-60 ℃, under the condition of spray time 5-50 second, aluminium foil is carried out to the chemical conversion processing, and use 120 ℃ of online drying plants to dry 35 seconds; (2) hot pressing of hot sealing layer material is compound: mass concentration is respectively to 10% maleic anhydride grafted polyethylene (percent grafting 5%), 35% metallocene PE, 52% polyethylene, 1% antioxidant and 2% anti-blocking agent and adds in proportion high-speed mixer to mix, with double screw extruder, extruded, the chemical conversion of using heat pressing process that the hot sealing layer material is uniformly coated on to aluminium foil is laminated; (3) dry type of nylon layer material is compound: composite prepared by step (2), evenly be coated with polyurethane aluminium foil adhesive specially, and carry out the compound compound aluminium foil material that makes with nylon layer after solvent evaporates; (4) compound aluminium foil material is put into to 60-80 ℃ of baking room and carried out maturation process 12-24h, cut, check, put in storage.
Embodiment 2
A kind of environment friendly non-halogen can be cold stamping shaped compound aluminium foil material, structure and thickness from outside to inside are followed successively by: 15-25 μ m nylon layer 1,3 μ m polyurethane sticking layers 2,40-60 μ m aluminium foil layer 3,0.2-3 μ m chemical conversion layer 4 and 10-20 μ m thermoplastic polyurethane hot sealing layer 5.By following processing step and technological parameter, prepare: (1) aluminium foil chemical conversion is processed: the chemical converting agent that is equipped with following concentration: ammonium titanium fluoride 10g/L, phytic acid 16g/L, silica gel 30g/L, the PVA(degree of polymerization 1400) 50g/L, regulate and keep pH value=5.3 with NaOH, at first clean the aluminium foil surface greasy dirt with ethyl acetate, then use spreader with 10mg/m
2coating weight aluminium foil is carried out to the chemical conversion processing, and use 120 ℃ of hot air circulation wind of online drying plant to dry 35 seconds; The collocation method wiring solution-forming that silane coupler is provided by manufacturer, be coated on plasma method the one side that aluminium foil transforms, and again dries; (2) hot pressing of hot sealing layer material is compound: thermoplastic polyurethane is extruded with double screw extruder, and the chemical conversion of using heat pressing process that the hot sealing layer material is uniformly coated on to aluminium foil is laminated; (3) dry type of nylon layer material is compound: composite prepared by step (2), evenly be coated with polyurethane aluminium foil adhesive specially, and carry out the compound compound aluminium foil material that makes with nylon layer after solvent evaporates; (4) compound aluminium foil material is put into to 60-80 ℃ of baking room and carried out maturation process 12-24h, cut, check, put in storage.
Embodiment 3
A kind of environment friendly non-halogen can be cold stamping shaped compound aluminium foil material, structure and thickness from outside to inside are followed successively by: 25 μ m nylon layer 1,3 μ m polyurethane sticking layer 2,50 μ m aluminium foil layer 3,3 μ m chemical conversion layer 4 and 15 μ m thermoplastic polyurethane hot sealing layers 5.By following processing step and technological parameter, prepare: (1) aluminium foil chemical conversion is processed: the chemical converting agent that is equipped with following concentration: ammonium titanium fluoride 10g/L, phytic acid 16g/L, silica gel 30g/L, the PVA(degree of polymerization 1400) 50g/L, regulate and keep pH value=5.3 with NaOH, at first clean the aluminium foil surface greasy dirt with ethyl acetate, then use spreader with 10mg/m
2coating weight aluminium foil is carried out to the chemical conversion processing, and use 120 ℃ of hot air circulation wind of online drying plant to dry 35 seconds; (2) hot pressing of hot sealing layer material is compound: thermoplastic polyurethane is extruded with double screw extruder, and the chemical conversion of using heat pressing process that the hot sealing layer material is uniformly coated on to aluminium foil is laminated; (3) dry type of nylon layer material is compound: composite prepared by step (2), evenly be coated with polyurethane aluminium foil adhesive specially, and carry out the compound compound aluminium foil material that makes with nylon layer after solvent evaporates; (4) compound aluminium foil material is put into to 60-80 ℃ of baking room and carried out maturation process 12-24h, cut, check, put in storage.
Embodiment 4
A kind of environment friendly non-halogen can be cold stamping shaped compound aluminium foil material, structure and thickness from outside to inside are followed successively by: 30 μ m nylon layer 1,2 μ m polyurethane sticking layer 2,80 μ m aluminium foil layer 3,10 μ m chemical conversion layer 4 and 10 μ m sarin resin hot sealing layers 5.By following processing step and technological parameter, prepare: (1) aluminium foil chemical conversion is processed: the chemical converting agent that is equipped with following concentration: ammonium titanium fluoride 10g/L, phytic acid 16g/L, silica gel 30g/L, the PVA(degree of polymerization 1400) 50g/L, regulate and keep pH value=5.3 with NaOH, at first clean the aluminium foil surface greasy dirt with ethyl acetate, then use spreader with 10mg/m
2coating weight aluminium foil is carried out to the chemical conversion processing, and use 120 ℃ of hot air circulation wind of online drying plant to dry 35 seconds; (2) hot pressing of hot sealing layer material is compound: the sarin resin is extruded with double screw extruder, and the chemical conversion of using heat pressing process that the hot sealing layer material is uniformly coated on to aluminium foil is laminated; (3) dry type of nylon layer material is compound: composite prepared by step (2), evenly be coated with polyurethane aluminium foil adhesive specially, and carry out the compound compound aluminium foil material that makes with nylon layer after solvent evaporates; (4) compound aluminium foil material is put into to 60-80 ℃ of baking room and carried out maturation process 12-24h, cut, check, put in storage.
Embodiment 5
A kind of environment friendly non-halogen can be cold stamping shaped compound aluminium foil material, structure and thickness from outside to inside are followed successively by: 15 μ m nylon layer 1,6 μ m polyurethane sticking layer 2,25 μ m aluminium foil layer 3,0.2 μ m chemical conversion layer 4 and 35 μ m thermoplastic polyurethane hot sealing layers 5.By following processing step and technological parameter, prepare: (1) aluminium foil chemical conversion is processed: the chemical converting agent that is equipped with following concentration: ammonium titanium fluoride 10g/L, phytic acid 16g/L, silica gel 30g/L, the PVA(degree of polymerization 1400) 50g/L, regulate and keep pH value=5.3 with NaOH, at first clean the aluminium foil surface greasy dirt with ethyl acetate, then use spreader with 10mg/m
2coating weight aluminium foil is carried out to the chemical conversion processing, and use 120 ℃ of hot air circulation wind of online drying plant to dry 35 seconds; (2) hot pressing of hot sealing layer material is compound: thermoplastic polyurethane is extruded with double screw extruder, and the chemical conversion of using heat pressing process that the hot sealing layer material is uniformly coated on to aluminium foil is laminated; (3) dry type of nylon layer material is compound: composite prepared by step (2), evenly be coated with polyurethane aluminium foil adhesive specially, and carry out the compound compound aluminium foil material that makes with nylon layer after solvent evaporates; (4) compound aluminium foil material is put into to 60～80 ℃ of baking rooms and carried out maturation process 12～24h, cut, check, put in storage.
Main quality standard and the assay method of compound aluminium foil material prepared by embodiment of the present invention 1-5 are as follows:
1, peel strength (nylon/aluminium foil): >=10N/15mm GB 8808
2, peel strength (aluminium foil/hot sealing layer) >=7N/15mm GB 8808
3, the cold punching degree of depth: >=6.5mm field measurement
4, barrier property :≤0.5cm3/(m224h0.1MPa) GB 1308
Above demonstration and described basic principle of the present invention and principal character and advantage of the present invention.Those skilled in the art should understand; the present invention is not restricted to the described embodiments; that in above-described embodiment and specification, describes just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the claimed scope of the invention.The claimed scope of the present invention is defined by appending claims and equivalent thereof.
Claims (4)
1. the preparation method that an environment friendly non-halogen can cold stamping shaped compound aluminium foil material, it is characterized in that comprising the following steps: (1) aluminium foil chemical conversion is processed, and adopts tannic acid facture, phytic acid coating with silane coupler promotion law or organosilan method, aluminium foil to be carried out to chemical treatment and form conversion coating on aluminium foil layer; (2) adopt heat pressing process the hot sealing layer material to be coated on equably on the conversion coating of aluminium foil; (3) aluminium foil surface of the composite prepared by step (2) is coated with polyurethane aluminium foil adhesive specially equably, after solvent evaporates, with nylon layer, carries out the compound compound aluminium foil material that makes; (4) compound aluminium foil material made is put into to 60-80 ℃ of baking room and heat-treated 12-24h, cut, check, put in storage, wherein nylon layer adopts and extends nylon, aluminium foil layer adopts O type aluminium foil, hot sealing layer adopts one or more in modified poly ethylene, modified polypropene or thermoplastic elastomer (TPE), and described thermoplastic elastomer (TPE) is thermoplastic polyurethane, sarin resin, polyethylene enhancing sarin resin, POE, SBC, TPV or thermoplastic polyester elastomer block copolymer Hytrel.
2. the preparation method that environment friendly non-halogen according to claim 1 can cold stamping shaped compound aluminium foil material, the detailed process that it is characterized in that tannic acid facture in described aluminium foil chemical conversion processing procedure is: the chemical converting agent that is equipped with following concentration: tannic acid 8.2g/L, phosphoric acid 0.04g/L, F-0.4g/L, Ti salt 0.05g/L, regulate and keep pH value=4.9 with NaOH, at first clean the aluminium foil surface greasy dirt with ethyl acetate, then at conversion temperature 30-60 ℃, under the condition of spray time 5-50 second, aluminium foil is carried out to the chemical conversion processing, and use 120 ℃ of oven dry of online drying plant.
3. the preparation method that environment friendly non-halogen according to claim 1 can cold stamping shaped compound aluminium foil material, it is characterized in that in described aluminium foil chemical conversion processing procedure, the phytic acid coating with the detailed process of silane coupler promotion law is: the chemical converting agent that is equipped with following concentration: ammonium titanium fluoride 10g/L, phytic acid 16g/L, silica gel 30g/L, the PVA(degree of polymerization 1400) 50g/L, regulate and keep pH value=5.3 with NaOH, at first clean the aluminium foil surface greasy dirt with ethyl acetate, then use spreader with 10mg/m
2coating weight aluminium foil is carried out to the chemical conversion processing, and use 120 ℃ of hot air circulation wind of online drying plant to dry, the collocation method wiring solution-forming that silane coupler is provided by manufacturer, be coated on the one side of aluminium foil conversion coating with plasma method, again dry.
4. the preparation method that environment friendly non-halogen according to claim 1 can cold stamping shaped compound aluminium foil material, the detailed process that it is characterized in that organosilan method in described aluminium foil chemical conversion processing procedure is: the chemical converting agent that is equipped with following concentration: ammonium titanium fluoride 10g/L, phytic acid 16g/L, silica gel 30g/L, the PVA(degree of polymerization 1400) 50g/L, regulate and keep pH value=5.3 with NaOH, at first clean the aluminium foil surface greasy dirt with ethyl acetate, then use spreader with 10mg/m
2coating weight aluminium foil is carried out to the chemical conversion processing, and use 120 ℃ of hot air circulation wind of online drying plant to dry.
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