CN1934004A - Synthetic resin container with high gas barrier performance - Google Patents
Synthetic resin container with high gas barrier performance Download PDFInfo
- Publication number
- CN1934004A CN1934004A CN 200580009547 CN200580009547A CN1934004A CN 1934004 A CN1934004 A CN 1934004A CN 200580009547 CN200580009547 CN 200580009547 CN 200580009547 A CN200580009547 A CN 200580009547A CN 1934004 A CN1934004 A CN 1934004A
- Authority
- CN
- China
- Prior art keywords
- film
- gas barrier
- barrier performance
- synthetic resin
- aforementioned
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Landscapes
- Laminated Bodies (AREA)
- Details Of Rigid Or Semi-Rigid Containers (AREA)
Abstract
Disclosed is a container made of a synthetic resin which has a coating (2) with high gas barrier performance on the inner and/or outer surface of a container main body. The coating (2) is composed of a multilayer film including at least a gas barrier film (2a) and a coating film (2b) which is arranged on the outermost side. The coating film (2b) arranged on the outermost side exhibits water repellency having a contact angle with water of 80-100 1/2 . Each film (2a, 2b) is formed by vapor deposition and has a refractive index of 1.3-1.6.
Description
Technical field
The present invention relates to a kind of polyethylene terephthalate (polyethylene terephthalate, PET) system bottle, particularly relating to a kind of is the synthetic resin container with high gas barrier performance of representative with the PET bottle, it prevents this container of gas permeation, prevent that particularly oxygen from seeing through, stable with the quality of guaranteeing content.
Background technology
In the last few years,, handled, be used more by plastic blowing (blow) container for making the tank capacity that holds belly wash, wine, oil, soy sauce etc. from discarded, carrying, recycling viewpoints such as (recycling).This container is compared with the glass container, because it can not avoid gas permeations such as oxygen and carbon dioxide, so the quality time limit of content, just shelf life (shelf-life) can be shorter.
As the technology of dealing with this type of problem, for example open in the 2000-109076 communique and propose the Japanese Patent spy, utilize the coverlay (SiO of evaporation or sputter (sputtering) coating (coating) high gas barrier performance at the bottle inner face
x).
Container according to above-mentioned existing known techniques making, compare with the container that does not have to implement to film, it can make the oxygen barrier performance improve more than the several times, but especially when surpassing under 80 ℃ the situation in container the filling content, the problem then inevitable (infer and caused by blocking the film crackle) that the original gas barrier performance that has of container is low need be improved at this point.
In addition,, particularly implement Water-heating shower (shower) when carrying out the sterilization processing of content, then can cause gas barrier performance low at container outer surface for the container that the high gas barrier performance coverlay is configured in container outer surface.
Summary of the invention
The objective of the invention is to, when a kind of filling high temperature content is provided and under the situation when accepting the processing of heat such as Water-heating shower, expose at high temperature, still can keep the synthetic resin container of the novelty of high gas barrier performance state even if container is inside and outside.
The object of the invention to solve the technical problems realizes by the following technical solutions.A kind of synthetic resin container according to the present invention's proposition with high gas barrier performance, the coverlay that on vessel inside face and/or outside face, has high gas barrier performance, its aforementioned coverlay is made of the laminated film by overlay film that contains the gas barrier performance film at least and be positioned at face side, being positioned at this rete by the face side of overlay film, to have angle of contact with water be 80～100 ° water-proofness, each rete of aforementioned each film of formation utilizes evaporation and forms, and its ratio of refraction is in 1.3～1.6 scope.
At this, what is called is positioned at by the face side of overlay film and means: no matter the inside face of vessel, or outside face is provided with under the situation of coverlay, all is set at the position of the face side of gas barrier performance film by overlay film, and cover this gas barrier performance film.
By technique scheme, the synthetic resin container that the present invention has high gas barrier performance has following advantage at least:
According to the present invention, owing to the gas barrier performance film on vessel inside face and/or outside face and by overlay film, be to utilize at this by the laminated film of the superficial layer configuration of overlay film, even if filling high temperature content, or applying processing by Water-heating shower, the gas barrier performance of container can not be adversely affected yet.Particularly by the vessel inside face and and the outside face both laminated film be set make gas barrier performance to improve more.
In container, with gas barrier performance film and comparatively desirable by the overlay film configuration that adjoins each other by said structure.In addition, it is the siliconoxide of major component that the gas barrier performance film is become with the monox, and making by overlay film becomes comparatively ideal of organic system silicon compound layer.
Between aforementioned laminated film and vessel the most surperficial, can dispose the base station film of forming by the organo-silicon compound layer.
Above-mentioned explanation only is the general introduction of technical solution of the present invention, for can clearer understanding technological means of the present invention, and can be implemented according to the content of specification sheets, and for above-mentioned and other purposes, feature and advantage of the present invention can be become apparent, below especially exemplified by preferred embodiment, and conjunction with figs., be described in detail as follows.
Description of drawings
Fig. 1 is shown as the section-drawing of main portion of the container of an embodiment of the present invention.
Fig. 2 is shown as the section-drawing of main portion of the container of another embodiment of the present invention.
Fig. 3 is shown as the comparison diagram of oxygen transit dose and BIF value.
1: the wall portion of vessel
2: the gas barrier performance coverlay
2a: siliconoxide
2b: organic system silicon compound layer
2c: organic system silicon compound layer
The specific embodiment
Reach technological means and the effect that predetermined goal of the invention is taked for further setting forth the present invention, below in conjunction with accompanying drawing and preferred embodiment, to its specific embodiment of the synthetic resin container with high gas barrier performance, structure, feature and the effect thereof that foundation the present invention proposes, describe in detail as after.
See also shown in Figure 1ly, Fig. 1 has shown polyethylene terephthalate (polyethylene terephthalate, PET) the main portion scheme drawing of resin container that utilizes diaxon to extend blowing technique in one embodiment of this invention and be shaped.
Reference number 1 is that it prevents that gas (particularly oxygen and carbon dioxide etc.) from seeing through in container or outside the container at the high gas barrier performance coverlay of the inside face setting of wall portion 1 for wall portion, the numeral 2 that constitutes vessel.
In Fig. 1, coverlay 2 is with silicon oxide compounds (SiO
x) be major component, it is by being formed with the organo-silicon compound layer 2b that is positioned at the surface of siliconoxide 2a in abutting connection with siliconoxide (mainly preventing the layer with barrier performance of the gas permeation) 2a of configuration with wall portion 1.
In the face side of the aforementioned siliconoxide 2a with high gas barrier performance, by aforementioned organic system silicon compound layer 2b is set, even and if make that filling high temperature content still can be kept the high gas barrier performance state in container.
In 2 the rete of forming covered film, siliconoxide 2a is by silicon oxide compounds (SiO
x) and the cmpd formed by silicon, carbon, hydrogen, oxygen at least (based on the layer of monox) constituted, organic system silicon compound layer 2b is made of the cmpd that silicon, carbon, hydrogen, oxygen are formed at least.
Be that the angle of contact of above-mentioned organic system silicon compound layer 2b and water is 80～100 °, therefore becomes the film with high water-proofness in 20～40 ° the scope with respect to angle of contact at above-mentioned siliconoxide 2a and water.Seeing through and making the angle of contact of the water that is positioned at the superficial film of coverlay 2 is 80～100 °, even if suppose under the situation that the hydrophilic layer of interlayer configuration etc. cracks, moisture is invaded to this crackle, and the moisture of this intrusion can not make crackle expansion etc., can suppress the low of gas barrier performance thus.
Each the thin-film refractive index value that constitutes each film is 1.3～1.6.Because the refractive index value of each rete is set in 1.3～1.6 scope, so can keep the good transparency of container.
See also shown in Figure 2ly, Fig. 2 has shown the another embodiment of the present invention that has disposed as the organic system silicon compound layer 2c of base station film between vessel wall portion 1 and siliconoxide 2a.
Organic system silicon compound 2c is the cmpd of being made up of silicon, carbon, hydrogen, oxygen at least.Compare with the two tunic situations of this organic system silicon compound layer 2c not, make organic system silicon compound layer 2c in the middle of two tunics, will make higher gas barrier performance become possibility.Its reason can be speculated as the polyethylene terephthalate of siliconoxide 2a and vessel, and (polyethylene terephthalate, the PET) adherence between can improve by making marginal organic system silicon compound layer 2c.Even and if have impact to wait effect when becoming the organic system silicon compound layer 2b film forming of superficial layer, crackle etc. also becomes and is difficult to produce on siliconoxide 2a.
At above-mentioned siliconoxide 2a, organic system silicon compound layer 2b, in the film forming processing procedure of 2c, can suitably adjust kind, gas flow and high-frequency (RF) output of gas, promptly can form various films, be not particularly limited for this point.
In addition, the gas barrier performance film, structure is such as described above by overlay film and base station film, be respectively the film that constitutes by simple layer also can, for the laminated film that piles up by plural layer also can, be not particularly limited for this point.
Not inside and outside the tubular container, forming base station film, gas barrier performance film in order from wall portion 1 beginning and by overlay film under the situation of the laminated film of three layers of such coverings, the adherence that is used for the gas barrier performance film on this base station film can be applicable to useful organic system silicon compound layer, at this moment, make the proportion of composing of base station film and, can make the phenomenon that the using gases kind increases when vapour deposition method is handled disappear by under the proportion of composing of the overlay film membrance casting condition much at one.
Embodiment
Seeking the PET bottle inside face of heat-resistingization, use Plasma Enhanced Chemical Vapor Deposition (PECVD) (the Plasma Chemical Vapor Deposition of high-frequency pulse ripple (pulse), plasma CVD) forms by overlay film, and investigate with regard to oxygen barrier performance (oxygen transit dose and moisture moisture permeability).
Going up the pulsed discharge condition of using in Plasma Enhanced Chemical Vapor Deposition (PECVD) (plasma CVD) in addition is: On:0.1sec, Off:0.1sec.
Table 1 shows the result who has by the bottle of the laminated film that PET (inner wall part)/organic system silicon compound layer/siliconoxide/the organic system silicon compound layer is formed.Table 2 shows the result of the bottle that siliconoxide only is set.Table 3 shows the result who has by the bottle of the laminated film that PET (inner wall part)/organic system silicon compound layer/siliconoxide is formed.And table 4 shows the result who has by the bottle of the laminated film that PET (inner wall part)/siliconoxide/the organic system silicon compound layer is formed.
In addition, " DEPO " in the table is that discharge time, (for example it was under 8 the situation, 8 seconds meaning of indicating impulse ripple discharge), " HMDSO " is hexamethyldisiloxane (hexamethyldisiloxane), " sccm " of gas flow be 0 ℃ with an atmospheric pressure state under, the gas flow that flow through in 1 minute (cc).Also have, the ratio of " ratio of components of unstrpped gas is " HMDSO, oxygen, nitrogen, the argon gas mixed states of gas such as (argon), " 40 ℃-75% RH of moisture permeability " are the temperature and the relative humidity of keeping environment, and " BIF " be the barrier performance improvement rate (Barrier Improvement Factor) with the comparison of film forming product not.
Table 1
| Test item | Membrance casting condition | Thickness () | Angle of contact θ (°) | The oxygen transit dose | 40 ℃-75%RH of moisture permeability | Appendix | |||||||||||||
| Gas flow (sccm) | The ratio of components of unstrpped gas (%) | ||||||||||||||||||
| 3 layers of film forming | RF exports (W) | DEP Scc | HM DSO | Oxygen | Argon gas | Si | O | C | H | Ar | Each container of cc/day | BIF | Each container of g/day | BIF | |||||
| Three layers laminated film | Ground floor | 300 | 8 | 20.0 | 2 | 20 | 7 | 4 | 21 | 64 | 4 | 1197 | 95.6 | Not filling | 0.0019 | 10.8 | 0.0235 | 1.79 | Be fit to example |
| The second layer | 450 | 12 | 5.0 | 20 | - | 6 | 26 | 17 | 51 | 0 | 91 ℃ of fillings | 0.0024 | 8.6 | 0.0320 | 1.31 | ||||
| The 3rd layer | 300 | 8 | 20.0 | - | 20 | 7 | 4 | 21 | 64 | 4 | |||||||||
Table 2
| Test item | Membrance casting condition | Thickness () | Angle of contact θ (°) | The oxygen transit dose | 40 ℃-75%RH of moisture permeability | Appendix | |||||||||||||
| Gas flow (sccm) | The ratio of components of unstrpped gas (%) | ||||||||||||||||||
| - | RF exports (W) | DEP O(Se c) | HMDS O | Oxygen | Argon gas | Si | O | C | H | Ar | Each container of cc/day | BIF | Each container of g/day | BIF | |||||
| Monofilm (siliconoxide) | - | 450 | 12 | 5.0 | 20 | - | 6 | 26 | 17 | 51 | 0 | 215 | 30.0 | Not filling | 0.0016 | 13.3 | 0.0331 | 1.28 | Comparative example |
| After 91 ℃ of fillings | 0.0149 | 1.4 | 0.0408 | 1.03 | |||||||||||||||
Table 3
| Test item | Membrance casting condition | Thickness () | Angle of contact θ (°) | The oxygen transit dose | 40 ℃-75%RH of moisture permeability | Appendix | |||||||||||||
| Gas flow (sccm) | The ratio of components of unstrpped gas (%) | ||||||||||||||||||
| Two layers of film forming | RF exports (W) | DEP O (Sec) | HMDS O | Oxygen | Argon gas | Si | O | C | H | Ar | Each container of cc/day | BIF | Each container of g/day | BIF | |||||
| Two layers laminated film | Ground floor | 300 | 8 | 20.0 | - | 30 | 7 | 4 | 21 | 63 | 5 | 806 | 30.0 | Not filling | 0.0018 | 11.3 | 0.0250 | 1.68 | Comparative example |
| The second layer | 450 | 16 | 5.0 | 33 | - | 5 | 35 | 16 | 45 | 0 | After 91 ℃ of fillings | 0.0155 | 1.3 | 0.0410 | 1.03 | ||||
Table 4
| Test item | Membrance casting condition | Thickness () | Angle of contact θ (°) | The oxygen transit dose | 40 ℃-75%RH of moisture permeability | Appendix | |||||||||||||
| Gas flow (sccm) | The ratio of components of unstrpped gas (%) | ||||||||||||||||||
| Two layers of film forming | RF output | DEP O (Sec | HM DSO | Oxygen | Argon gas | Si | O | C | H | Ar | Each container of cc/day | BIF | Each container of g/day | BIF | |||||
| **Two layers laminated film | Ground floor | 450 | 12 | 5.0 | 20 | - | 6 | 26 | 17 | 51 | 0 | 634 | 93.5 | Not filling | 0.0076 | 2.7 | - | - | Be fit to example |
| The second layer | 300 | 8 | 20.0 | - | 20 | 7 | 4 | 21 | 64 | 4 | After 91 ℃ of fillings | 0.0086 | 2.5 | - | - | ||||
*Silicon oxide layer+organic system silicon layer
See also shown in Figure 3ly, Fig. 3 is the scheme drawing that has shown that oxygen transit dose and BIF value with table 1～4 compare.Can obviously know from Fig. 3, at relevant container of the present invention (be fit to example) even in the content of 91 ℃ of fillings also be subjected to hardly to influence by heat is caused, and can confirm that the present invention can keep high gas barrier performance.
From the above, be exposed under the hi-heat situation inside and outside making container by high temperature filling or Water-heating shower etc., also can keep the synthetic resin container of high gas barrier performance even the present invention can provide.
The above, it only is preferred embodiment of the present invention, be not that the present invention is done any pro forma restriction, though the present invention discloses as above with preferred embodiment, yet be not in order to limit the present invention, any those skilled in the art, in not breaking away from the technical solution of the present invention scope, when the technology contents that can utilize above-mentioned announcement is made a little change or is modified to the equivalent embodiment of equivalent variations, in every case be the content that does not break away from technical solution of the present invention, according to technical spirit of the present invention to any simple modification that above embodiment did, equivalent variations and modification all still belong in the scope of technical solution of the present invention.
Claims (5)
1, a kind of synthetic resin container with high gas barrier performance, it is characterized in that: on the inside face of vessel and/or outside face, have the high gas barrier performance coverlay, aforementioned coverlay is constituted by the laminated film of overlay film by containing the gas barrier performance film at least and being positioned at face side, being positioned at this rete by the face side of overlay film, to have angle of contact with water be 80～100 ° water-proofness, each rete of aforementioned each film of formation utilizes evaporation and forms, and its ratio of refraction is in 1.3～1.6 scope.
2, the synthetic resin container with high gas barrier performance according to claim 1 is characterized in that wherein said aforementioned gas barrier performance film and aforementioned by the overlay film configuration that adjoins each other.
3, the synthetic resin container with high gas barrier performance according to claim 1 and 2 is characterized in that having the base station film between wherein said aforementioned laminated film and vessel the most surperficial.
4, the synthetic resin container with high gas barrier performance according to claim 1 and 2 is characterized in that wherein said aforementioned gas barrier performance film is to be the siliconoxide of major component with the monox, and aforementioned be the organic system silicon compound layer by overlay film.
5, the synthetic resin container with high gas barrier performance according to claim 4 is characterized in that wherein said aforementioned laminated film and vessel dispose the base station film between the most surperficial, and this base station film is made up of the organo-silicon compound layer.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP093586/2004 | 2004-03-26 | ||
| JP2004093586 | 2004-03-26 | ||
| JP023684/2005 | 2005-01-31 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1934004A true CN1934004A (en) | 2007-03-21 |
Family
ID=37879313
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200580009547 Pending CN1934004A (en) | 2004-03-26 | 2005-03-23 | Synthetic resin container with high gas barrier performance |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1934004A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102026880B (en) * | 2008-03-31 | 2014-01-01 | 株式会社吉野工业所 | Container made of synthetic resin having excellent barrier properties |
-
2005
- 2005-03-23 CN CN 200580009547 patent/CN1934004A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102026880B (en) * | 2008-03-31 | 2014-01-01 | 株式会社吉野工业所 | Container made of synthetic resin having excellent barrier properties |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP1921015B1 (en) | Synthetic resin container with high barrier capability | |
| US9903012B2 (en) | Film formation method and film formation apparatus | |
| JP4158265B2 (en) | Plastic container manufacturing method and container | |
| WO2012133687A1 (en) | Vapor-deposited film having barrier performance | |
| JP4711285B2 (en) | Synthetic resin container with high gas barrier properties | |
| US20030194517A1 (en) | Coating compositions containing a silane additive and structures coated therewith | |
| JP2008023934A (en) | Gas barrier laminate | |
| CN1934004A (en) | Synthetic resin container with high gas barrier performance | |
| JP5351204B2 (en) | Method for producing gas barrier film having hot water resistance and gas barrier film having hot water resistance | |
| KR20140067079A (en) | Multilayer structure offering improved impermeability to gases | |
| JP4106931B2 (en) | Transparent gas barrier thin film coating film | |
| JP4046155B2 (en) | Gas barrier film | |
| JP2013193267A (en) | Gas barrier plastic film and method of manufacturing the same | |
| US20150255749A1 (en) | Gas permeation barriers and methods of making the same | |
| US20240183021A1 (en) | Laminate and method of manufacturing laminate | |
| JP2007261134A (en) | Antistatic barrier film | |
| JP2005313504A (en) | Gas-barrier film | |
| JP2005059537A (en) | Gas-barrier film and its production method | |
| JP4819190B2 (en) | Method for producing gas barrier film having hot water resistance and gas barrier film having hot water resistance | |
| JP5427821B2 (en) | Gas barrier film manufacturing method and gas barrier film | |
| JP4435397B2 (en) | Transparent barrier film | |
| JP3965028B2 (en) | Method for manufacturing silicon oxide film | |
| JP2005280718A (en) | Synthetic resin container having high gas barrier property | |
| JP2001341225A (en) | Transparent gas barrier laminated film and method for manufacturing the same | |
| JPH11245327A (en) | Protective film and forming method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |