JP3484550B2 - Retort packaging film - Google Patents

Retort packaging film

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Publication number
JP3484550B2
JP3484550B2 JP33537794A JP33537794A JP3484550B2 JP 3484550 B2 JP3484550 B2 JP 3484550B2 JP 33537794 A JP33537794 A JP 33537794A JP 33537794 A JP33537794 A JP 33537794A JP 3484550 B2 JP3484550 B2 JP 3484550B2
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Japan
Prior art keywords
film
layer
siox
retort
laminated
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Expired - Fee Related
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JP33537794A
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Japanese (ja)
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JPH08174748A (en
Inventor
隆則 大星
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大日本印刷株式会社
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Priority to JP33537794A priority Critical patent/JP3484550B2/en
Publication of JPH08174748A publication Critical patent/JPH08174748A/en
Application granted granted Critical
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Anticipated expiration legal-status Critical
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Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a film for flexible packaging which can be retorted and has a transparent barrier layer which is colorless, transparent and excellent in durability. About. 2. Description of the Related Art Conventionally, a flexible packaging film that can withstand a retort treatment at 100 to 135 ° C. is provided with a picture layer, if necessary, on a stretched polyester or stretched nylon film that can withstand the temperature of the retort treatment. A film in which a heat seal resin layer mainly composed of high-density polyethylene or polypropylene is laminated via a reaction-curable heat-resistant adhesive layer has been used. [0003] However, the conventional retort packaging film using an aluminum foil as a barrier layer has a problem in that the contents are not visible and the sales promotion effect is poor. On the other hand, in order to make the contents visible, a patterned layer is provided on the stretched polyester or stretched nylon film, if necessary, excluding the opaque aluminum foil, and a heat sealing resin layer containing high-density polyethylene or polypropylene as a main component, Films laminated via a reaction-curable heat-resistant adhesive layer have also been used, but have the problem that they are inferior in barrier properties such as oxygen and flavor and have a limited shelf life as compared with metal aluminum foil. . Further, a technique of a film for retort packaging using a plastic film provided with a vapor-deposited metal oxide having excellent oxygen barrier properties as a barrier layer has been disclosed. However, the vapor deposition layer providing the barrier property is not colorless,
The metal oxide deposited layer, which changes the color of the contents or has a small spreadability, cannot follow the expansion and contraction of the film during retort treatment, especially when the film is extended, and cracks may occur in the deposited layer. There is a problem that it occurs. Similarly, when making a bag, there is a problem that the heat seal cannot easily follow the expansion and contraction of the film due to the heat and pressure of the heat seal, and the heat seal tends to crack. In addition, since the silicon oxide vapor deposition layer is also formed with a thickness of 500 ° or more, there is a problem that the content is slightly yellowish brown and the contents appear to be discolored. SUMMARY OF THE INVENTION The present invention relates to a colorless and transparent barrier film, and a base film provided with an ultra-fine thin film layer mainly composed of transparent silicon oxide, which is rich in extensibility and flexibility. This constitutes a retort packaging film using the above. Further, it is an object of the present invention to provide a film for retort packaging in which the film does not crack due to expansion and contraction and impact during processing, bag making, filling, and retort treatment, thereby reducing the barrier property. [0006] In order to achieve the above object, a retort packaging film of the present invention has a transparent barrier layer provided on at least one surface of a base film by a plasma chemical vapor deposition method. The transparent barrier layer is a continuous layer containing a compound of one or more of silicon oxide and carbon, hydrogen, silicon, and oxygen (hereinafter, referred to as an SiOx layer in this specification). , And a film provided with a SiOx layer is abbreviated as a SiOx film.) Then, a compound composed of one or more of carbon, hydrogen, silicon, and oxygen contained in the SiOx layer decreases from the surface of the SiOx layer toward the interface with the base film. Things. [0007] The retort packaging film of the present invention is shown in FIG.
As shown in FIG. 1, a SiOx film 21 having a SiOx layer 2 provided on a base film 1 and a heat-sealing resin layer 6 are laminated by providing a reaction-curable adhesive layer 4.
The retort packaging film shown in FIG.
The film 21 is formed by sequentially laminating the SiOx layer 2, the adhesive layer 4, the reinforcing film 3, the adhesive layer 4, and the heat sealing resin layer 6 on the film 21. And the reinforcing film 3
Although not shown, a picture layer can be provided on one of the surfaces as necessary. Since the SiOx layer is difficult to follow the elongation of the film, it is preferable that the layer does not expand or contract by heat or steam such as retort treatment.
In the case of the above high-temperature retort, as shown in FIG.
The Ox layer 2 is provided on the stretched polyester film 11 which is hardly affected by heat and steam, and the stretched polyester film 31 which is a water-resistant reinforcing film for the purpose of protecting the SiOx layer 2 is made of a reaction-curable adhesive having excellent water resistance. 4, a retort packaging film in which the heat-sealing strength is strengthened and the stretched nylon film 32, which is a reinforcing film to be a printing film, and the heat-sealing resin layer 6 are laminated. In this case, printing is performed on the polyester 31 for the reinforcing film used to protect the SiOx layer, or the stretched nylon film 32 is used.
Or can be omitted. The substrate film on which the SiOx layer is provided can be provided on a flexible film of stretched polyester, stretched nylon, stretched polypropylene or the like. Also,
As shown in FIG. 4, an unstretched film can be used as the base film, for example, by laminating the SiOx layer 2 provided on one side of the heat seal resin layer 6 and another reinforcing film 3. Preferably, it is a stretched polyester film which can be formed into a relatively thin film and has excellent transparency. The organic silicon compounds used for forming the SiOx layer include 1,1,3,3-tetramethyldisiloxane, hexamethyldisiloxane, vinylmethyldisiloxane,
Methyltrimethoxysilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, phenyltrimethoxysilane, methyltrimethoxysilane, It can be selected from methyltriethoxysilane and octamethylcyclotetrasiloxane, and is preferably 1,1,3,3-tetramethyldisiloxane or hexamethyldisiloxane. The organic silicon compound, which is a liquid, is vaporized, and a raw material gas obtained by mixing oxygen gas and helium and / or argon, which are inert gases, is subjected to plasma-enhanced chemical vapor deposition provided with a film for adhering SiOx. To form a 60-500 ° SiOx layer. The SiOx layer thus formed in the continuous layer contains a compound or a mixture of one or more of carbon, hydrogen, silicon and oxygen. Specific examples thereof include a mixture of silicon and hydrogen comprising a silyl group or a silylene group, and silanol. The content of these compounds is 0.1 to 40% by weight, preferably 5 to 20% by weight of the SiOx layer. If the content is less than 0.1% by weight, the impact resistance and spreadability of the barrier layer become insufficient, cracks are generated due to bending or the like, and high barrier properties cannot be maintained. On the other hand, if it exceeds 40% by weight, the barrier properties are undesirably reduced. The concentration of a compound formed from one or more of carbon, hydrogen, silicon, and oxygen contained in the SiOx layer is SiO 2
The surface of the x-layer is formed to be high and decrease from the surface toward the interface with the base film. For this reason, the impact resistance on the outermost surface where cracks are most likely to occur is improved, and the adhesion between the substrate film and the SiOx layer becomes strong. [0013] The reinforcing film of the film for retort packaging is selected depending on its purpose and application.
In general, a film that can increase the heat seal strength at the same time as printing the picture layer is used. For example, a transparent film such as stretched polyester, stretched nylon, or stretched polypropylene is used. When the strength of the bag is particularly required, the reinforcing film 3 is laminated as shown in FIG. 2 or, for example, a stretched polyester 31 and a stretched nylon film 32 as a two-layered reinforcing film via an adhesive. The laminated retort packaging film shown in FIG. 3 can be obtained. Conversely, when the strength as a bag is not required, the SiOx layer and the heat sealing resin layer shown in FIGS. 1, 4 and 5 where the reinforcing film is omitted are directly laminated without providing a film layer, for retort packaging. Films can also be constructed. When this reinforcing film is omitted, the picture layer 5 can be provided on the SiOx layer 2 if necessary, as shown in FIG. The pattern layer is formed by gravure rotary printing, which is suitable for a step of laminating a SiOx film or a heat sealing resin layer. The ink used is film,
As long as it is suitable for post-processing and post-treatment, a hot water-resistant gravure ink using a usual two-component curable urethane-based resin as a main colorant and a pigment having excellent hot water resistance as a coloring agent can be used. The adhesive layer is made of polyether, polyester, or the like generally used for retort packaging films.
Alternatively, the adhesive is appropriately selected from two-part reactive adhesives of 1 to 7 types of polyurethane and polyisocyanate. The heat-sealing resin layer can be formed by laminating an unstretched film such as high-density polyethylene or polypropylene used for a normal retort packaging film using the above-mentioned reaction-curable adhesive. From the viewpoint of transparency, it is preferable to laminate the unstretched polypropylene film by dry lamination. Then, when the bag is subjected to retort treatment, polyisobutylene such that the heat-sealed portion withstands expansion and contraction due to fluctuations in heat pressure
Synthetic rubber such as polybutylene may be added. The thickness of the SiOx layer of the SiOx film formed as described above is 60 to 500.degree.
High flexibility and oxygen permeability of 1 cc / m 2 · 2
The water vapor permeability is 4 g or less and 1 g / m 2 · 24 h or less. A compound comprising one or more elements of silicon oxide and carbon, hydrogen, silicon, and oxygen contained in the SiOx layer has flexibility, which is an action of imparting physical properties similar to an organic polymer compound. It has something. Therefore, the SiOx layer is rich in spreadability, has a high adhesive strength between the SiOx film and the film, and acts to prevent cracking when laminating the SiOx film with another film. And, when the laminated film is put to practical use as a bag, and bag making, filling of contents, retort treatment, and logistics transportation of packaged products, there is no generation of cracks due to expansion and contraction of the film, and oxygen or water vapor is generated. The barrier property is not reduced. Embodiments will be described with reference to the drawings. Example 1 A raw material gas obtained by vaporizing hexamethyldisiloxane on polyester 11 which is a 12 μm-thick base film and mixing hexamethyldisiloxane: oxygen gas: helium gas = 1: 9: 8 was used as a raw material gas. 2 was formed at a thickness of 150 ° to form a SiOx film 21 shown in FIG. The SiOx layer 2 is G. FIG. Scientific ESCA (Electron Spectoroscopy)
As a result of analyzing the cross-sectional layer using for Chemical Analysis, it was confirmed that the carbon atom content decreased from the surface of the film toward the interface of the base film.
Next, a pattern layer 5 is provided on the SiOx layer 2 of the SiOx film 21 by gravure printing with a normal retort ink, and an adhesive layer 4 is further provided, and an unstretched polypropylene film 61 is laminated as a heat seal resin layer, A retort packaging film was constructed. [Embodiment 2] As in Embodiment 1, 12 μm
m of a polyester film 11 with a SiOx layer 2 of 200
The SiOx film 21 shown in FIG. 6 was formed with a thickness of Å. On the other hand, a pattern layer 5 is provided on one side of a 12 μm-thick stretched polyester film 31 by a gravure printing method using a usual retort ink, and the other side and a SiOx layer 2 are provided.
Provided with an adhesive layer 4 made of a polyurethane-based adhesive
An Ox film 21 is laminated by dry lamination, and an adhesive layer 4 made of a polyurethane-based adhesive is further provided on the picture layer 5 of the stretched polyester film 31. An unstretched polypropylene film 61 having a thickness of 60 μm, which is a heat sealing resin layer. Were laminated to form a retort packaging film shown in FIG. Comparative Example Using silicon oxide as a raw material, 1
The vapor-deposited layer 2 of the vapor-deposited film provided on the stretched polyester film 11 with a thickness of 200 mm, and the stretched polyester film 31, the picture layer 5, the adhesive layer 4, and the heat sill resin layer 61 as the reinforcing films as in Example 2. A retort packaging film laminated in this order was constructed. With respect to the film for retort packaging constituted in Examples and Comparative Examples and the bag formed from the film, a bag filled with a mixture of tap water and salad oil 1: 1 was subjected to a retort treatment at 120 ° C. for 20 minutes. Table 1 shows the evaluation results of the physical properties of the obtained bag as a film. (Test method) ・ Oxygen permeability is measured by OXTRAN manufactured by MOCON.
Measured at a temperature of 23 ° C and a humidity of 90% RH.・ The water vapor permeability is PERMATRAN manufactured by MOCON
Is measured under the conditions of a temperature of 40 ° C. and a humidity of 90% RH. -The bending test measures the oxygen permeability and the water vapor permeability under the same conditions as described above after 1000 times of the bending test using a gelbo flex tester manufactured by Tester Sangyo Co., Ltd. The adhesive strength was measured by measuring the adhesive strength between the reinforcing film 3 and the SiOx film 21 shown in FIG. 2, confirming the peeled portion, and measuring the peel strength according to JIS K7128. [Table 1] In the examples, the peeled portions when the adhesive strength was measured were all between the SiOx layer and the ink or adhesive layer. Further, in the comparative example, peeling was partially observed between the base film and the vapor deposition layer. Table 2 shows the results of a visual sensory test and a measurement of the light transmittance at 500 nm of the coloring of the retort packaging films of the Examples and Comparative Examples. [Table 2] Evaluation of coloring of film Since the present invention is configured as described above, it has the following effects. Si of the SiOx film formed as described above
The thickness of the Ox layer is from 60 to 500 °, with little coloration, high flexibility, and oxygen permeability of 1 cc / m 2 · 24 h.
Hereinafter, the water vapor permeability is 1 g / m 2 · 24 h or less.
A compound or a mixture of one or more of carbon, hydrogen, silicon and oxygen contained in the SiOx layer has an action of imparting properties similar to those of the organic polymer compound. Therefore, the SiOx layer has excellent spreadability, has high adhesive strength between the SiOx layer and the film, and has few cracks generated when laminating the SiOx film with another film. And, when the laminated film is put to practical use as a bag and the bag making, filling of contents, retort treatment, and logistics transportation of the packaged product are performed, the SiOx layer is peeled off between the films of the laminated film or the laminated film is laminated. No decrease in adhesive strength between films,
Cracks do not lower the oxygen or water vapor barrier properties.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic cross-sectional view showing a laminated structure of a retort packaging film of the present invention. FIG. 2 is a schematic sectional view showing another laminated structure of the retort packaging film of the present invention. FIG. 3 is a schematic sectional view showing another laminated structure of the retort packaging film of the present invention. FIG. 4 is a schematic sectional view showing another laminated structure of the retort packaging film of the present invention. FIG. 5 is a schematic cross-sectional view showing a laminated structure according to an example of the present invention. FIG. 6 is a schematic sectional view showing a laminated structure according to another embodiment of the present invention. [Description of Signs] 1 Base film 11 Stretched polyester film (base film) 12 Stretched polypropylene film (base film) 2 SiOx layer 21 SiOx film 3 Reinforcement film 31 Stretched polyester film (Reinforcement film) 32 Stretched nylon film (Reinforcement) Film) 4 Adhesive layer 5 Picture layer 6 Heat seal resin layer 61 Polypropylene (heat seal resin layer)

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification code FI C23C 16/40 C23C 16/40 16/50 16/50

Claims (1)

  1. (57) [Claims] [Claim 1] At least one surface of a substrate film ,
    A mixture of organic silicon compound, oxygen gas and inert gas
    Gas, using a plasma-enhanced chemical vapor deposition method.
    A light barrier layer, and the transparent barrier layer
    And a silicon oxide layer,
    Contains carbon atoms and fills the substrate from the film surface.
    The above carbon atom content decreases toward the interface of the
    A retort packaging film comprising a continuous layer .
JP33537794A 1994-12-22 1994-12-22 Retort packaging film Expired - Fee Related JP3484550B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP33537794A JP3484550B2 (en) 1994-12-22 1994-12-22 Retort packaging film

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Application Number Priority Date Filing Date Title
JP33537794A JP3484550B2 (en) 1994-12-22 1994-12-22 Retort packaging film

Publications (2)

Publication Number Publication Date
JPH08174748A JPH08174748A (en) 1996-07-09
JP3484550B2 true JP3484550B2 (en) 2004-01-06

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Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4569982B2 (en) * 1999-11-15 2010-10-27 大日本印刷株式会社 Laminated packaging for boil or retort processing
TW570876B (en) * 2001-05-11 2004-01-11 Toyo Seikan Kaisha Ltd Silicon oxide film
US7015640B2 (en) * 2002-09-11 2006-03-21 General Electric Company Diffusion barrier coatings having graded compositions and devices incorporating the same
AU2003271138B2 (en) * 2002-10-09 2008-07-10 Toyo Seikan Kaisha, Ltd. Method of forming metal oxide film and microwave power source unit for use in the method
JP4919583B2 (en) * 2004-02-17 2012-04-18 大日本印刷株式会社 Hydrogen peroxide barrier film and laminate using the same.
JP4944993B2 (en) * 2008-08-19 2012-06-06 リンテック株式会社 Molded body, manufacturing method thereof, electronic device member, and electronic device
JP5379530B2 (en) 2009-03-26 2013-12-25 リンテック株式会社 Molded body, manufacturing method thereof, electronic device member and electronic device
US20120108761A1 (en) * 2009-05-22 2012-05-03 Lintec Corporation Formed article, method of producing same, electronic device member, and electronic device
EP2433980B1 (en) * 2009-05-22 2019-07-10 LINTEC Corporation Molded object, process for producing same, member for electronic device, and electronic device
JP5697230B2 (en) 2010-03-31 2015-04-08 リンテック株式会社 Molded body, manufacturing method thereof, member for electronic device, and electronic device
EP2607412A4 (en) 2010-08-20 2014-04-30 Lintec Corp Molding, production method therefor, part for electronic devices and electronic device
TWI457235B (en) 2010-09-21 2014-10-21 Lintec Corp A gas barrier film, a manufacturing method thereof, an electronic device element, and an electronic device
TWI535561B (en) 2010-09-21 2016-06-01 Lintec Corp A molded body, a manufacturing method thereof, an electronic device element, and an electronic device
JP6157973B2 (en) * 2013-07-30 2017-07-05 福島印刷工業株式会社 Structure of wrapping material for boil and retort sterilization and method for producing sachets using the wrapping material

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