CN1276120C - Producing process for high-separation vacuum aluminium-plating thin film - Google Patents
Producing process for high-separation vacuum aluminium-plating thin film Download PDFInfo
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- CN1276120C CN1276120C CN 200310112661 CN200310112661A CN1276120C CN 1276120 C CN1276120 C CN 1276120C CN 200310112661 CN200310112661 CN 200310112661 CN 200310112661 A CN200310112661 A CN 200310112661A CN 1276120 C CN1276120 C CN 1276120C
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- thin film
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- 238000000034 method Methods 0.000 title claims description 17
- 230000008569 process Effects 0.000 title claims description 8
- 238000007747 plating Methods 0.000 title claims 2
- 239000010409 thin film Substances 0.000 title abstract 5
- 238000000926 separation method Methods 0.000 title 1
- 230000004888 barrier function Effects 0.000 claims abstract description 29
- 238000004381 surface treatment Methods 0.000 claims abstract description 10
- 230000000694 effects Effects 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims description 20
- 239000000758 substrate Substances 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 230000005684 electric field Effects 0.000 claims description 9
- 238000005269 aluminizing Methods 0.000 claims description 5
- 238000007738 vacuum evaporation Methods 0.000 claims description 3
- 238000002294 plasma sputter deposition Methods 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims 1
- 239000010408 film Substances 0.000 abstract description 39
- 238000005516 engineering process Methods 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 2
- 210000002381 plasma Anatomy 0.000 description 32
- 229910052782 aluminium Inorganic materials 0.000 description 19
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 19
- 239000007789 gas Substances 0.000 description 13
- 239000004411 aluminium Substances 0.000 description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 10
- 238000003475 lamination Methods 0.000 description 8
- 230000000149 penetrating effect Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000011104 metalized film Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- -1 polypropylene Polymers 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000005025 cast polypropylene Substances 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Physical Vapour Deposition (AREA)
Abstract
The present invention relates to technology for producing a high barrier vacuum aluminized thin film, which is characterized in that after plasma is sputtered onto the surface of a thin film in the vacuum environment, the thin film is evaporated in vacuum. Compared with a vacuum aluminized film without plasma surface treatment under the same technological conditions, the barrier properties of the thin film are enhanced by 3 to 5 times. The technology of the present invention has the advantages of obvious effect, low cost and no pollution.
Description
Technical field:
The claimed technical scheme of the present invention belongs to the metallized production technique of plastics film, specifically belongs to make high-barrier vacuum aluminized film technical field.
Background technology:
High-barrier vacuum aluminized film (HB-VMPET, HB-VMCPP) belongs to the novel material Application Areas, is a kind of wrapping material with high obstructing performance, is widely used on the composite packaging of food, beverage, medicine, makeup etc.It is formed through vacuum aluminum-coated post-treatment by flexible packages, has good metal gloss, effectiveness, and static resistance and opacifying property especially have preferably choke, resistance is moist, has improved tens times even hundreds of times before its barrier property ratio is aluminized.Simultaneously, its tooling cost is low, and multiple well-formedness is good, except self can doing the wrapping material, can also with multiple film process be combined into new, the better matrix material of performance.
At present, disclosed vacuum aluminized film production technique is to be that the disclosed cast polypropylene vacuum aluminized film of CN87103355 technology is representative with the China Patent No., this technology is substrate plastic film to be sent to carry out vacuum evaporation under the vacuum environment, and promptly the steam output of vacuum tightness, temperature and aluminium by the control vacuum environment makes and plates the layer of aluminum film on the plastics film.Want to improve the barrier of metallized film according to the method, solve with the method that improves aluminum layer thickness usually.But barrier is not to be directly proportional with thickness of coating in production practice, and when aluminum layer thickness increased, density, the aluminium lamination of aluminium lamination were loss of adhesion, and the little pore of coating increases, and causes barrier to reduce.So product oxygen transmission rate 〉=2.0cc/m of producing of processing method based on this in general
2.day.latm, rate of perviousness 〉=1.0g/m
2.day.Along with the progress of society, improving constantly of people's quality of life paid much attention to commodity health, safety etc., improves the reliability of packing, the quality guaranteed period of prolongation commodity, becomes the developing focus of domestic and international packaging field.If can make the high-barrier vacuum aluminized film possess excellent more barrier property, will prolong the quality guaranteed period and the shelf-lives of commodity greatly, and will further expand the Application Areas and the market requirement.
Summary of the invention:
Technical problem to be solved by this invention provides a kind of product that produces than prior art and has the more production technique of the production vacuum aluminized film of high obstructing performance.
The scheme of technical solution problem of the present invention is: the production technique of high-barrier vacuum aluminized film, elder generation behind the surface of film substrate, carries out vacuum evaporation to film with plasma sputtering again in vacuum environment.
The present invention is based on such thinking and proposes: because the barrier of product is not to be directly proportional with thickness of coating, when aluminum layer thickness increased, the density aluminium lamination of aluminium lamination was loss of adhesion, and the little pore of coating increases, and caused barrier to reduce.After by plasma body substrate surface being handled can: (1), remove the pollutent and the entrap bubble of the substrate surface of aluminizing, effectively avoid discharging and making aluminium lamination produce small pin hole at the angry body of the process application for issue of aluminizing, strengthen the compactness of aluminium lamination, improved the barrier property of metallized film.(2), can be so that form the polar group of some amount on the plastics film surface aggregate thing molecular chain, as-CO ,-OH ,-COOH ,-NH etc., can greatly improve the substrate surface performance.Substrate surface after treatment is easy and form firm, fine and close bonding force with Van der Waals force, hydrogen bond or chemical bond, makes aluminium lamination sticking power significantly improve, thereby has significantly improved the barrier property of metallized film.
Using plasma surface treatment law technology in film is aluminized process, plasma body is under given conditions, makes the gas partial ionization and the non-coacervated system that produces, and it is by neutral atom or molecule, the atom of excited state or molecule, free radical, electronics or negative ion, positive ion or photon are formed.In the process of aluminizing, film is placed the energetic plasma zone of plasma surface processor, promptly in a side on the processed surface of film, one group of cathode tube under the effect of midfrequent AC voltage is installed, and the magnetron that is provided with near the film another side.Gas produces a large amount of energetic plasmas by negative electrode.Because the action of a magnetic field that film the opposing party magnetron produces, plasma body moves towards film surface, by sputter and impact the surface of film is handled.
By repeatedly practice, be fit to aluminize every index of base material and the every processing parameter in the process of aluminizing below the formulation.
The strength of electric field of plasma body is between 7-9V/m.The plasma body strength of electric field here is meant the size of power suffered in the magnetic field of plasma body between two hollow cathodes, and it has reflected the energy size of plasma body.Result of study shows that along with the increase that produces the plasma apparatus power input, plasma body strength of electric field increases, and barrier is also along with corresponding raising.The finished product barrier decreases on the contrary when power input is increased to certain value, this is because during the too high Cement Composite Treated by Plasma film of energy, can cause the surface to form etching, and surfaceness increases, the coating uniformity coefficient is bad, thereby the strength of electric field optimum range is between 7-9V/m.
It is more suitable to use air to carry out surface treatment as the plasma gas type to non-polar material during as base material.This is because N
2Be a kind of active gas, handle non-polar material, can generate-NH isoreactivity group with it, and N in the air
2Content is higher, and raw material sources are extensive.This material is representative with the polypropylene film, and its amount of using on wrapping material also is bigger.And use O during as base material at polar material
2With Ar be 1 according to volume ratio: the amount of 8-11 is mixed the back, and to carry out surface treatment as the plasma gas type more suitable.This material is representative with the polyester film, and its amount of using on wrapping material also is bigger.Because Ar can only clear up pollutent, steam and the gas etc. of substrate surface, aluminium lamination produces micropore when avoiding al deposition, to strengthen barrier; Closely-related with vacuum aluminized film sticking power, barrier etc. is the generation of oxy radical, therefore mixing a certain proportion of oxygen in the body stops as reaction gas, its plasma body and material surface reaction produce oxy radical, as-OH ,-CO ,-COOH etc., its barrier property of metallized film after treatment is higher.
When we determined that the film travelling speed is 200-500m/min, the gas flow of plasma body was at 250-300ml/min; Vacuum tightness is 2.0 * 10
-4～4.0 * 10
-4Between the Torr.This processing parameter can guarantee that plasma body can be to follow-up vacuum aluminum-coated bad effect to the surface treatment of film substrate, and the gauge control of vacuum aluminium coated layer is in suitable scope, and the economy and the product that make production have maximum have maximum barrier.
The present invention has used plasma body that the surface of metallized film base material is handled, and has effectively improved the barrier property of Al metallizing Fool, and the Al metallizing Fool of producing without plasma surface treatment under the same processing condition of its barrier improves 3～5 times.It is remarkable to have effect, and cost is low, free of contamination advantage.
Embodiment:
Each embodiment selects following starting material for use:
A group: base material PET film, thickness 12 μ m; Plasma species: O
2(purity 〉=99.9%) and Ar (purity 〉=99.99%), O
2With the Ar volume ratio be 1: 9
B group: base material CPP film, thickness 25 μ m; Plasma species: air.
Each embodiment all steps on the DYDP-5040F type continuous vacuum aluminum-spraying machine equipment the scholar of section energetically and produces.Above 2-3 rice before base material is sent to evaporation source one group of frequency towards substrate surface being installed is 50Hz, voltage is the hollow cathode under the effect of 380V midfrequent AC voltage, film another side top is provided with the ground connection magnetron, the parameter of magnetron: operating frequency: 20-25KHZ, maximum current: 7A, voltage: 10-15KV, magneticstrength is 50-1000 Gauss.
Testing method and test condition are carried out according to the GB2918-82 standard, steam penetrating capacity: 38 ℃ of temperature, humidity 90%; Oxygen transit dose: 23 ℃ of temperature, humidity 0%.Tensile strength, elongation at break, percent thermal shrinkage, sticking power are according to the QY/HNDP31-2001 standard testing.
Steam penetrating capacity tester: U.S. Mocon 3/61 type.Oxygen transit dose tester: U.S. Mocon 2/61 type.
Table one is that film travelling speed 300m/min, vacuum tightness are 3.0 * 10
-4During Torr, strength of electric field is 8V/m, the barrier of the high-barrier vacuum aluminized film of producing under the gas flow different situations of plasma body.
| Test group | Gas flow ml/min; | Aluminum layer thickness μ m | Tensile strength MPa 〉= | Elongation at break % 〉= | Percent thermal shrinkage %≤ | Sticking power | Steam penetrating capacity (g/m 2.24h) ≤ | Oxygen transit dose (cc/m 2.24h. 0.1MPa)≤ |
| A | 200 | 0.04 | 195 | 100％ | 1.5 | One-level | 0.46 | 0.55 |
| 250 | 0.04 | 190 | 100％ | 1.5 | One-level | 0.23 | 0.40 | |
| 300 | 0.04 | 200 | 100％ | 1.5 | One-level | 0.26 | 0.43 | |
| 350 | 0.04 | 190 | 100％ | 1.5 | One-level | 0.52 | 0.58 | |
| a | / | 0.04 | 190 | 100％ | 1.5 | Secondary | 1.5 | 2.5 |
| B | 200 | 0.04 | 40 | 600％ | / | One-level | 1.6 | 1.1 |
| 250 | 0.04 | 45 | 600％ | / | One-level | 0.82 | 0.62 | |
| 300 | 0.04 | 45 | 600％ | / | One-level | 0.76 | 0.58 | |
| 350 | 0.04 | 40 | 600％ | / | One-level | 1.4 | 0.86 | |
| b | / | 0.04 | 40 | 100％ | / | Secondary | 3.2 | 2.8 |
A, b are the control experiment of not passing through plasma surface treatment under the same processing condition in the last table.Last table shows, will substantially exceed index in the same old way through the product barrier after the Cement Composite Treated by Plasma.Illustrate that simultaneously the plasma flow amount is influential to the thickness and the final barrier of product aluminium coated.The plasma body airshed should be controlled in the reasonable scope under the condition that the film travelling speed is determined.
Table two is that the gas flow of film travelling speed 300m/min, plasma body is 250ml/min; The barrier of the high-barrier vacuum aluminized film of under different vacuum degree condition, producing.
| Test group | Vacuum tightness * 10 -4Tor | Steam penetrating capacity (g/m 2.24h)≤ | Oxygen transit dose (cc/m 2.24h.0. 1MPa)≤ | |
| A | 1 | 4.5 | 0.20 | 0.34 |
| 2 | 3.5 | 0.26 | 0.45 | |
| 3 | 2.5 | 0.21 | 0.35 | |
| 4 | 1.8 | 1.2 | 2.3 | |
| B | 1 | 4.5 | 0.52 | 0.42 |
| 2 | 4.0 | 0.67 | 0.56 | |
| 3 | 2.0 | 0.55 | 0.52 | |
| 4 | 1.8 | 3.4 | 2.8 | |
Last table shows that vacuum tightness has influence on the thickness of aluminium coated and the barrier of product.Therefore need control in the hope of rationally economic parameter the vacuum tightness of vacuum chamber.
Table three is the barrier of the identical high-barrier vacuum aluminized film of producing of other condition of A3 in the table two and B3 under different strength of electric field.
| Test group | Strength of electric field V/m | Steam penetrating capacity (g/m 2.24h)≤ | Oxygen transit dose (cc/m 2.24h.0. 1Mpa)≤ | |
| A | 5 | 10 | 0.62 | 0.85 |
| 6 | 9 | 0.23 | 0.43 | |
| 7 | 8 | 0.12 | 0.35 | |
| 8 | 7 | 0.58 | 0.74 | |
| B | 5 | 10 | 1.01 | 1.32 |
| 6 | 9 | 0.54 | 0.56 | |
| 7 | 8 | 0.51 | 0.52 | |
| 8 | 7 | 1.34 | 0.98 | |
Last table shows, the too high or too low effect of plasma body to substrate surface treatment that all can reduce of strength of electric field.
Table four is the identical barrier of selecting the high-barrier vacuum aluminized film that dissimilar plasma bodys produce for use with other condition of A2 in the table two.
| Gas type | Steam penetrating capacity (g/m 2.24h)≤ | Oxygen transit dose (cc/m 2.24h.0. 1Mpa)≤ |
| Air | 0.35 | 0.62 |
| Oxygen+argon gas | 0.38 | 0.54 |
| Argon gas | 0.45 | 0.74 |
Last table shows that the plasma body of single type does not have the A2 treatment effect good to the effect as a result of substrate surface treatment.
Table five for table two in the identical O that selects for use of other condition of A2
2With Ar according to the barrier of different volumes than the high-barrier vacuum aluminized film of producing after mixing.
| O 2: Ar (volume ratio) | Steam penetrating capacity (g/m 2.24h)≤ | Oxygen transit dose (cc/m 2.24h.0. 1Mpa)≤ |
| 1∶7 | 0.23 | 0.38 |
| 1∶8 | 0.18 | 0.34 |
| 1∶10 | 0.21 | 0.44 |
| 1∶11 | 0.23 | 0.46 |
| 1∶12 | 0.35 | 0.56 |
Last table shows O
2With Ar according to 1: the different volumes of 8-11 is better than the barrier of the high-barrier vacuum aluminized film of producing after mixing.
Claims (2)
1, the production technique of high-barrier vacuum aluminized film for arrive the surface of polarity film substrate with plasma sputtering earlier in vacuum environment after, is carried out vacuum evaporation to film again, it is characterized in that: in surface treatment process, use O
2With the Ar mixed gas as plasma gas, O
2With the volume ratio of Ar be 1: 8-11; In the process of aluminizing, film is placed the energetic plasma zone of plasma surface processor, promptly in the side on the processed surface of film, one group of cathode tube under the effect of midfrequent AC voltage is installed, and the magnetron of close film another side setting, the strength of electric field of plasma body is between 7-9V/m, and the film travelling speed is 200-500m/min, and the gas flow of plasma body is between 250-300ml/min; Vacuum tightness is 2.0 * 10
-4-4.0 * 10
-4Between the Torr.
2, the production technique of high-barrier vacuum aluminized film according to claim 1 is characterized in that: the base material of described high barrier aluminum-plating film is a polyester material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310112661 CN1276120C (en) | 2003-12-18 | 2003-12-18 | Producing process for high-separation vacuum aluminium-plating thin film |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310112661 CN1276120C (en) | 2003-12-18 | 2003-12-18 | Producing process for high-separation vacuum aluminium-plating thin film |
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|---|---|
| CN1552942A CN1552942A (en) | 2004-12-08 |
| CN1276120C true CN1276120C (en) | 2006-09-20 |
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|---|---|---|---|
| CN 200310112661 Expired - Lifetime CN1276120C (en) | 2003-12-18 | 2003-12-18 | Producing process for high-separation vacuum aluminium-plating thin film |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102011013822A1 (en) * | 2011-03-14 | 2012-09-20 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Method for modifying a surface of a substrate by ion bombardment |
| CN102350829A (en) * | 2011-06-30 | 2012-02-15 | 黄山永新股份有限公司 | Composite film for candy packaging and preparation method thereof |
| US8846548B2 (en) * | 2013-01-09 | 2014-09-30 | Taiwan Semiconductor Manufacturing Company, Ltd. | Post-passivation interconnect structure and methods for forming the same |
| CN106756778A (en) * | 2016-12-27 | 2017-05-31 | 嘉兴鹏翔包装材料有限公司 | A kind of preparation method of the vacuum aluminized film of aluminium coated adhesive force high |
| CN108004519A (en) * | 2017-08-09 | 2018-05-08 | 嘉兴鹏翔包装材料有限公司 | Medicine is packed for high-barrier VMCPP method for manufacturing thin film and medicine and is packed for high-barrier VMCPP films automatically automatically |
| CN115651252A (en) * | 2022-11-05 | 2023-01-31 | 江苏宗亮新材料有限公司 | Aluminum-plated high-adhesion polypropylene film and preparation process thereof |
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2003
- 2003-12-18 CN CN 200310112661 patent/CN1276120C/en not_active Expired - Lifetime
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Assignee: GUANGZHOU NOVEL PACKAGING CO.,LTD. Assignor: Huangshan Novel Co.,Ltd. Contract record no.: 2010440000937 Denomination of invention: Producing process for high-separation vacuum aluminium-plating thin film Granted publication date: 20060920 License type: Exclusive License Open date: 20041208 Record date: 20100708 |
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