JP2007137438A - Pouch for boil retort - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a pouch for boil retort in which existence of a heating sterilization processing such as a boil processing and a retort processing can be accurately and simply confirmed and judged by viewing, which is excellent in filling and packaging suitability, content protecting suitability or the like and is excellent in beautifully decorativeness, which arouses consumers' purchasing interest without spoiling appearance of a packaging body, and which is useful for filling and packaging mainly not only boil retort eating and drinking articles or the like, but also oils and fats, frozen drinking and eating articles, drinking and eating articles for conservation, or the like. <P>SOLUTION: The pouch for boil retort is composed of a packaging bag prepared by using a laminated material constituted of a laminate of at least a drawn substrate film with a through-view part and a heat-sealable co-extruding and laminating film with a white layer to be made into a bag. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a boil / retort pouch. More specifically, the presence / absence of heat sterilization such as boil treatment or retort treatment can be confirmed and judged accurately and simply by visual inspection, suitability for filling and packaging, content protection suitability, etc. In addition to being excellent in cosmetics and appealing to consumers without damaging the appearance of the package, it is mainly used for boil and retort foods and drinks, oils and fats, frozen foods and drinks, preserved foods and drinks, The present invention relates to a boil / retort pouch useful for filling and packaging other items.

Conventionally, a laminated material is produced by arbitrarily laminating one or more of plastic film, metal foil, cellophane, etc., and then using the laminated material to produce a bag for packaging. Produced and then placed in the packaging bag, for example, as desired, such as curry, stew, soup, meat sauce, hamburger, meatball, sweet potato, oden, etc. A packaged semi-finished product is manufactured by filling and packaging foods and beverages and the like, and then the packaged semi-finished product is, for example, about 20-60 at a temperature, about 110 ° C. to 130 ° C., pressure, 1 to 3 kgf / cm ² · G. The retort-processed packaged food which consists of various forms is manufactured by performing the heat-pressurization process which consists of a retort process for about a minute. Further, instead of the retort treatment as described above, for example, a packaging semi-finished product is manufactured in the same manner as described above, and then the packaging semi-finished product is subjected to heat sterilization including, for example, a boil treatment at about 90 ° C. for about 30 minutes. Processing boiled foods, boiled food is manufactured.
Thus, in the boiled retort-processed packaged food as described above, in recent years, forgetting the boil-retort processing process or the like, or due to insufficient boil-retort processing, defective products frequently occur, for example, As a result, defective products such as the contents rot, etc. occur, and after the shipment from the manufacturer, there is a noise in the collection of the packaged product, and so-called boil / retort treatment process is frequently performed. It is the actual situation.
In order to solve the above-mentioned problem, for example, a method has been proposed in which an indicator label is attached to a packaging bag and the boil / retort treatment process is confirmed by discoloration. The method is unpreferable because it is a complicated and extra process for attaching a label or the like, and has a problem that the label is dropped.
In recent years, for example, a resin outer layer film, a base film, and a resin inner layer film are bonded together by an adhesive layer in this order, and a retort packaging sheet that encloses a product to be retorted is used. A retort wrapping material sheet, characterized in that a water vapor discoloration indicator ink layer at a sterilization temperature is formed on at least a part between the outer layer film and the base film, and The indicator ink layer is formed of any one of an ink containing a transition metal compound and sulfur and / or a sulfur compound, and an ink containing a monoazo dye and an organic acid and / or a metal salt thereof. A packaging sheet has been proposed (see, for example, Patent Document 1).
JP 2003-334897 A (claim)

However, in the packaging sheet according to the above-mentioned Patent Document 1, a transition metal compound, a sulfur compound, a monoazo dye, etc. constituting the indicator ink layer are used to prepare an ink composition, in its handling, etc. Is inconvenient in terms of workability, maintainability, and the like.
Moreover, the use of such transition metal compounds, sulfur compounds, monoazo dyes, etc. is also concerned about the influence on the contents.
Furthermore, the use of transition metal compounds, sulfur compounds, monoazo dyes, and the like as described above is extremely expensive because these materials are special, and this is reflected in costs and the like. There are also problems.
Therefore, the present invention can accurately and easily confirm and judge the presence or absence of heat sterilization treatment such as boil treatment or retort treatment, and is excellent in filling packaging suitability, content protection suitability, etc. Boil which is useful for filling and packaging mainly for boil and retort food and drink, fats and oils, frozen food and drink, preserved food and drink, etc. • To provide retort pouches.

As a result of various studies to improve the above problems, the present inventor has laminated at least a stretched base film having a see-through portion and a heat sealable coextruded laminated film having a white layer. And then, using this, making a bag to produce a packaging bag, and then, for example, curry, stew, soup, meat soot in the packaging bag. -A packaged semi-finished product is produced by filling and packaging desired foods and beverages such as sauce, hamburger, meatball, sushi, oden, etc .; Retort treatment for about 20 to 60 minutes at a temperature of about 130 ° C. to 130 ° C., pressure, 1 to 3 kgf / cm ² · G, or boil treatment for about 30 minutes at about 90 ° C. To produce a boiled and retorted packaged food. In the boiled / retort-processed packaged food, the pigments in the food / beverage products filled and packaged during the boil / retort treatment are transferred to a heat-sealable co-extruded laminated film having a white layer, and the pigment is transferred to the white layer. When the heat-sealable coextruded laminated film is dyed and thus seen through the see-through part of the stretched base film outside the packaging bag and having the see-through part, the dyeing state is visually observed. In this way, the presence or absence of heat sterilization treatment such as boil treatment or retort treatment can be confirmed and judged accurately and easily, and it is excellent in filling and packaging suitability, content protection suitability and the like. It excels in consumers' ability to purchase without compromising the appearance of the package. Filling mainly with boil and retort food and drink, fats and oils, frozen food and drink, preserved food and drink, etc. Wrap The present invention has been completed by finding a useful boil retort pouch.

  That is, the present invention uses a laminated material composed of at least a stretched base film having a see-through portion and a heat-sealable coextruded laminated film having a white layer, and forms the bag. The present invention relates to a boil / retort pouch characterized by comprising a packaging bag.

The boil / retort pouch according to the present invention has an advantage that the presence or absence of a heat sterilization treatment such as a boil treatment or a retort treatment can be easily confirmed and judged visually and accurately.
Moreover, the boil / retort pouch according to the present invention is made of a material widely used in packaging materials until now without using a special material such as a conventional indicator. There is no concern about the impact on the contents.
Furthermore, the boil / retort pouch according to the present invention is superior in filling and packaging suitability, content protection suitability, etc., and has excellent cosmetics, and evokes consumers' willingness to purchase without impairing the appearance of the package. It is useful for filling and packaging oils, frozen foods, preserved foods, etc., as well as boil and retort foods.

Hereinafter, the present invention will be described in more detail with reference to the drawings.
First, FIG. 1, FIG. 2, FIG. 3 and FIG. 4 are schematic sectional views showing an example of the layer structure of the laminated material constituting the boil / retort pouch according to the present invention, and FIG. FIG. 2 is a schematic perspective view showing an outline of the configuration of the packaging bag constituting the pouch for boil / retort according to the present invention produced by bag-making and using the laminated material according to the present invention shown in FIG. 6 is a boil / retort-treated packaging according to the present invention in which the contents are filled and packaged in a packaging bag constituting the boil / retort pouch according to the present invention shown in FIG. It is a schematic perspective view which shows the outline of the structure about foodstuffs.

  First, in the present invention, the laminated material constituting the boil / retort pouch according to the present invention will be described. The laminated material A constituting the boil / retort pouch according to the present invention is, for example, as shown in FIG. The basic structure includes at least a stretched base film 2 having a see-through portion 1 and a heat-sealable coextruded laminated film 4 having a white layer 3.

Thus, in the present invention, as a specific example of the laminated material constituting the boil / retort pouch according to the present invention, for example, as shown in FIG. In addition, a desired printed pattern 5 composed of characters, figures, patterns, symbols, etc. is provided and a non-printed pattern region 1a is provided at a desired position on the back surface of the stretched base film 2 as a see-through portion 1, Thus, in the present invention, as described above, the see-through portion 1 including the printed pattern 5 and the non-printed pattern region 1a is provided on the back surface of the stretched base film 2, and then the printed pattern 5 and the non-printed pattern region are provided. A laminated material A ₁ constituting a boil / retort pouch according to the present invention, which is formed by laminating a heat-sealable coextruded laminated film 4 having a white layer 3 on the surface of the see-through portion 1 made of la. It can be illustrated.

Moreover, in this invention, when another specific example is illustrated about the laminated material which comprises the pouch for boil retort which concerns on this invention, for example, as shown in FIG. For example, a desired printed pattern 5 made of, for example, characters, figures, pictures, symbols, and the like is provided on the back surface of the film, and a non-printed pattern region 1a is provided at a desired position on the back surface of the stretched substrate film 2, Thus, in the present invention, the transparent portion 1 comprising the printed pattern 5 and the non-printed pattern region 1a is provided on the back surface of the stretched base film 2 as described above, and then the printed pattern 5 is provided. A stretched resin film 7 having an inorganic oxide vapor-deposited film 6 is laminated on the surface of the see-through portion 1 composed of the non-printed pattern region 1a, and the stretched resin having the inorganic oxide vapor-deposited film 6 laminated as described above. On the surface of film 7, white Tosi - - arsenide has a layer 3 may be exemplified laminate A ₂ constituting a boiling or retorting pouch according to the present invention constructed by laminating Le of coextruded multilayer film 4.

Furthermore, in this invention, when another specific example is illustrated about the laminated material which comprises the pouch for boil retort which concerns on this invention, for example, as shown in FIG. Thus, on the surface of the inorganic oxide vapor deposition film 6 of the stretched resin film 7 having the inorganic oxide vapor deposition film 6 in the same manner as described above, For example, a desired printed pattern 5 composed of characters, figures, patterns, symbols, etc. is provided, and a desired portion of the surface of the inorganic oxide vapor-deposited film 6 of the stretched resin film 7 having the inorganic oxide vapor-deposited film 6 is provided. A non-printed pattern region 1a is provided as a see-through portion 1, and then a heat seal property having a white layer 3 on the surface of the see-through portion 1 composed of the printed pattern 5 and the non-printed pattern region 1a. Coextruded laminated film 4 is laminated The laminate A ₃ constituting a boiling or retorting pouch according to the present invention which form can be exemplified.

The above illustrations illustrate a few examples of the laminated material constituting the boil / retort pouch according to the present invention, and it goes without saying that the present invention is not limited thereto.
For example, although not shown, in the present invention, the printed pattern, the see-through portion, and the like can be provided on both the front and back surfaces of the stretched substrate film and the like.
In addition, although not shown in the drawings, in the present invention, the laminated material constituting the boil / retort pouch according to the present invention, in addition to the laminated material exemplified above, in addition to its packaging purpose, contents, etc., Other base materials can be arbitrarily selected and used, and a laminated material having an arbitrary layer structure can be manufactured and used.
Furthermore, although not shown in the drawings, in the present invention, for the laminated material constituting the boil / retort pouch according to the present invention, as a lamination method, for example, an anchor coating agent layer / melting with an anchor coating agent is used. Laminate by means of a melt extrusion laminating method in which lamination is carried out through an extruded resin layer, or a dry lamination method in which lamination is carried out by means of a laminating adhesive layer by means of a laminating adhesive, or both. Can be laminated together to produce a laminated material constituting the boil / retort pouch according to the present invention having various layer configurations.

  Next, in the present invention, the packaging material constituting the boil / retort pouch according to the present invention using the laminated material constituting the boil / retort pouch as described above and bag-making this will be described. As the packaging bag, for example, the laminated material A shown in FIG. 1 is used, and the packaging bag made from the laminated material A will be described as an example. As shown in FIG. , A are prepared, and the heat-sealable coextruded laminated films 4 and 4 having the white layer 3 positioned at the innermost layer are overlapped with each other facing each other, and thereafter, the end portions around the outer periphery thereof These three sides are heat sealed to form the heat seal portions 11, 11, 11 and the opening 12 to form the boil-retort pouch according to the present invention. The packaging bag B can be manufactured.

Thus, in the present invention, as shown in FIG. 6, the three-side seal type packaging bag B constituting the boil / retort pouch according to the present invention manufactured as described above is used, and the opening 12 thereof is used. From, for example, the contents 13 such as curry, stew, soup, meat sauce, hamburger, meatball, sweet potato, oden, etc. Next, the upper opening 12 is heat sealed to form the upper seal portion 14 and the like to produce a packaging semi-finished product C. Thereafter, the packaging semi-finished product C is treated with, for example, a temperature, 110 A retort-processed packaged food D having various forms can be produced by performing heat sterilization treatment or the like consisting of retort treatment for about 20 to 60 minutes at a temperature of about 130 ° C. to 130 ° C., pressure, 1 to 3 kgf / cm 2. It can be done.
In the present invention, instead of the retort treatment as described above, for example, a packaging semi-finished product similar to the above is manufactured, and then the packaging semi-finished product is boiled at about 90 ° C. for about 30 minutes. A boiled packaged food can be produced by applying a heat sterilization treatment or the like made of
In FIGS. 5 and 6, reference numeral 1 represents a fluoroscopic part.

Thus, in the present invention, in the boil / retort-processed packaged food as described above, the heat-sealable coextrusion in which the coloring matter or the like in the food / beverage product filled and packaged during the boil / retort process has a white layer. The dye is transferred to a laminated film, the dye dyes the heat-sealable coextruded laminated film having a white layer, and is outside the packaging bag constituting the boiled / retort-processed packaged food as described above. In addition, when seeing through the see-through part of the stretched substrate film having a see-through part, the dyed state can be easily visually confirmed, thereby confirming the presence or absence of heat sterilization treatment such as boil treatment or retort treatment. It can be easily confirmed and judged accurately and simply.
The above examples are examples of the boil / retort pouch according to the present invention, the boil / retort processed packaged food using the pouch, and the present invention is not limited thereto. is there.
For example, in the present invention, it is needless to say that the boil / retort pouch according to the present invention is not limited to the shape of the illustrated packaging bag shown above. Packaging bags having various forms such as a four-sided seal type, a self-supporting type, a gusset type, a square bottom type, a pillow type, and the like can be manufactured.
Further, in the present invention, the laminated material constituting the boil / retort pouch according to the present invention shown in FIG. 2, FIG. 3, FIG. 4 and the like is used. It is possible to manufacture packaging bags constituting retort pouches, boiled / retort-processed packaged foods, and the like.

Next, in the present invention, the material, the manufacturing method and the like constituting the retort pouch according to the present invention will be described. First, the stretched substrate film constituting the retort pouch according to the present invention will be described. As the film, since these are the basic materials constituting the retort pouch according to the present invention, heat resistance, slipperiness, resistance to heat, workability, etc. at the time of lamination or bag making, etc. A stretched resin film or sheet excellent in various physical properties such as pinhole property and others can be used.
In the present invention, the stretched resin film or sheet specifically includes, for example, polyolefin resins such as polyethylene resins or polypropylene resins, cyclic polyolefin resins, polystyrene resins, acrylonitrile-styrene. Copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), poly (meth) acrylic resin, polycarbonate resin, polyethylene terephthalate, polyethylene naphthalate, etc. Polyester resins, polyamide resins such as various nylon resins, polyurethane resins, acetal resins, cellulose resins, and other various resin films or sheets can be used.
Thus, as the resin film or sheet, any of stretched films stretched in a uniaxial direction or a biaxial direction can be used.
In the present invention, the thickness of the resin film or sheet may be a thickness that can be kept to the minimum necessary for strength, puncture resistance, rigidity, and the like. On the other hand, if it is too thin, the strength, puncture resistance, rigidity, etc. are lowered, which is not preferable.
In the present invention, for the reasons described above, about 10 μm to 100 μm, preferably about 12 μm to 50 μm is most desirable.
Thus, in the present invention, among the resin films or sheets as described above, in particular, a biaxially stretched polyester resin film having a thickness of about 9 to 30 μm, a biaxially stretched polyamide resin film, or It is preferable to use a biaxially stretched polypropylene resin film or the like.
In addition, in this invention, the extending | stretching resin film which has the vapor deposition film | membrane of the inorganic oxide mentioned later can be used similarly as an extending | stretching base film which comprises the boil retort pouch which concerns on this invention.

Next, in the present invention, as described above, the method for providing the see-through portion on the stretched substrate film as described above is, for example, printing using printing methods such as off-sec printing, gravure printing, transfer printing, and the like. A see-through portion can be formed by a method of providing a pattern region and a non-printed pattern region and using the non-printed pattern region as a see-through portion.
Alternatively, in the present invention, the see-through portion can be formed by a method of providing an image portion and a non-image portion using an ink jet method or the like, and using the non-image portion as a see-through portion.
In addition, methods such as cutting and others can also be used.

  Next, in the present invention, a heat-seal coextruded laminated film having a white layer constituting the retort pouch according to the present invention will be described. Specifically, for example, as shown in FIGS. 7 and 8, at least a transparent or translucent resin layer 21, a white resin layer 3, and a transparent or translucent resin layer 21 are sequentially laminated. A heat-sealable coextruded laminated film 4a having a white layer (FIG. 7), or at least a transparent or translucent resin layer 21, a white resin layer 3, a light-shielding black or gray resin layer 22, Further, a heat-seal coextruded laminated film 4b (FIG. 8) having a white layer in which transparent or translucent resin layers 21 are sequentially laminated can be used.

In the heat-sealable coextruded laminated film having the white layer according to the present invention, the transparent or translucent resin layer is melted by the action of heat and constitutes the laminated material according to the present invention. It has the effect of laminating and laminating each other with a stretched base film or a stretched resin film having an inorganic oxide.
Furthermore, in the present invention, the transparent or translucent resin layer uses the laminated material according to the present invention, forms a bag, and forms a boil / retort pouch according to the present invention. It melts by the action of heat and has the action of forming a seal part by fusing together.
Moreover, in the heat-sealable coextruded laminated film having a white layer according to the present invention, the white resin layer is basically a pigment in a food or drink filled and packaged during boil / retort processing. The dye is transferred to a heat-sealable coextruded laminated film having a white resin layer, and the dye dyes the white resin layer of the heat-shearable coextruded laminated film having a white resin layer. When it is outside the packaging bag constituting the boiled / retort-processed packaged food according to the invention and is seen through from the see-through part of the stretched base film having the see-through part, the dyed state can be easily visually confirmed. Thus, there is an effect that the presence or absence of the heat sterilization treatment such as the boil treatment or the retort treatment can be easily confirmed and determined accurately and easily.
Further, the white resin layer reflects or diffuses sunlight or fluorescent light from the sun or a fluorescent lamp and acts as a light-shielding or light-shielding layer that prevents the transmission thereof, and also has a light-shielding property described later. It acts as a protective layer or concealment layer for protecting or concealing a black or gray resin layer or the like.
Next, in the heat-sealable coextruded laminated film having a white layer according to the present invention, the light-shielding black or gray resin layer is basically synergistic with the white resin layer. It acts as a light-blocking or light-blocking layer that absorbs sunlight or fluorescent light from the sun or a fluorescent lamp and blocks its transmission.

Thus, in the present invention, the transparent or translucent resin layer constituting the heat-sealable coextruded laminated film having the white layer according to the present invention has, for example, a resin composition containing a polyolefin resin as a main component. A transparent or translucent resin layer according to the present invention can be formed using the product.
In the present invention, the white resin layer constituting the heat-sealable coextruded laminated film having the white layer according to the present invention as described above includes, for example, a polyolefin-based resin as a main component, and further, white A white resin layer according to the present invention is formed using a resin composition containing a pigment and having a white pigment content of 0.5 wt% to 30.0 wt% with respect to the polyolefin resin. Can be configured.
Next, in the present invention, the black or gray resin layer constituting the heat-sealable coextruded laminated film having the white layer according to the present invention contains, for example, a polyolefin-based resin as a main component, and further, black A resin composition containing a pigment and a black pigment content of 0.1 wt% to 20.0 wt% with respect to the adhesive polyolefin resin, or a polyolefin resin as a main component Furthermore, it contains a black pigment and a white pigment, and the content of the black pigment is 0.1 wt% to 20.0 wt% with respect to the polyolefin resin, and the content of the white pigment is The light-shielding black or gray resin layer according to the present invention can be constituted using a resin composition or the like comprising 1 to 30 times the black pigment content.

  In the above, as a polyolefin-based resin for forming a transparent or translucent resin layer, a white resin layer, a black or gray resin layer, etc. constituting the heat-sealable coextruded laminated film having a white layer according to the present invention Is a polyolefin-based resin that can be melted by heat and extruded from a T-die, such as low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear (linear) low-density polyethylene, metallocene catalyst Ethylene-α / olefin copolymer, polypropylene, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer Polymer, ethylene-propylene copolymer, methylpentene polymer, polyethylene, polypropylene Polyolefin resins having a heat seal property such as acid-modified polyolefin resins modified with unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic anhydride, fumaric acid, etc. 1 type (s) or 2 or more types can be used.

Thus, in the present invention, the polyolefin resin further includes ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene. It is preferable to use a polyethylene resin such as a copolymer with α-olefin such as 1-nonene, 1-decene, etc.
In the present invention, as the polyethylene resin, specifically, a copolymer of ethylene and 1-octene is preferably used from the viewpoint of the melt tension property of the polyethylene resin.
As the copolymer of ethylene and 1-octene, the melt flow rate (MFR) is in the range of 0.1 to 4.0 g / 10 min, and the density is 0.900 to 0.930 g. Those within the range of / cm ³ can be used.
In the above, if the melt flow rate (MFR) is less than 0.1 g / 10 min, it is not preferable because it causes an increase in resin pressure and causes the machine (film forming machine) to stop, and the melt flow rate ( If MFR) exceeds 4.0 g / 10 min, it is not preferable because the top blown inflation film formation becomes difficult. In addition, in the above, if the density is less than 0.900 g / cm ^3, it is not preferable because of a decrease in the stiffness (rigidity) of the entire light-shielding coextruded laminated film according to the present invention. If it exceeds 0.930 g / cm ³ , it is not preferable because of lack of suitability as a heat seal layer (heat seal material).

Further, in the present invention, as the polyolefin resin, it is preferable to use a polypropylene resin such as a homopolymer of propylene or a copolymer (copolymer) of propylene and an α-olefin such as ethylene. It is.
In addition, as said polypropylene resin, the block copolymer (copolymer) or the random copolymer (copolymer) is used especially, Furthermore, the random copolymer (copolymer) is used. Is preferable.
Thus, in the present invention, it is preferable to use a polypropylene resin that is excellent in melt tension, stretchability, etc., and has an inflation molding suitability described later, specifically, a polypropylene resin. It is preferable to use those in which long chain branching is introduced into the main chain to increase the tension in the molten state.
In the present invention, specifically, as a polypropylene resin excellent in melt tension and stretchability, a polypropylene resin composed of a block or random copolymer of propylene and ethylene or propylene and 1-octene is used. Is preferred.
Thus, in the polypropylene resin composed of a block or random copolymer of propylene and ethylene or propylene and 1-octene, the density is about 0.9 [g / cm ³ ]. The rate (MFR) is in the range of about 0.1 to 2.0 [g / 10 min], and the melt tension is in the range of 100 [mN] or more (10 [cN] or more). Can be used.
Further, in the above, when the melt flow rate (MFR) is less than 0.1 [g / 10 minutes], the resin pressure increases during resin extrusion, giving a large load to the film forming machine, etc. Those exceeding 2.0 [g / 10 min] are not suitable for the top blowing inflation film formation method and are not preferred because they do not blow upward. Furthermore, in the above, when the melt tension is less than 100 [mN] (less than 10 [cN]), it is not preferable because it is not suitable for the top blowing inflation film forming method.

Next, in the present invention, a white resin layer constituting the heat-sealable coextruded laminated film having a white layer according to the present invention, and further, a white pigment forming a light-shielding gray resin layer, etc. For example, specifically, it is desirable to use, for example, a mixture of one or more kinds of colorants such as various inorganic and organic dyes and pigments of white type.
In the present invention, as the above-mentioned various white type inorganic or organic dyes, pigments and other colorants, for example, basic lead carbonate, basic lead sulfate, basic lead silicate, zinc white, sulfide One or more of white pigments such as zinc, lithopone, antimony trioxide, anatase-type titanium oxide, rutile-type titanium oxide, calcium carbonate, zinc oxide, barium sulfate, etc. can be used.
Thus, the amount of white pigment used is preferably about 1 to 30 times the black pigment content when forming a light-shielding gray resin layer, and the white resin layer is formed. When used, it is used by adding about 0.5% to 30.0% by weight, preferably about 3.0% to 20.0% by weight, based on the polyolefin resin forming the resin composition. It is desirable to do.

In the present invention, the black pigment forming the light-shielding black or gray resin layer constituting the heat-sealable coextruded laminated film having the white layer according to the present invention may be, for example, the sun or a fluorescent lamp. Absorbs sunlight or fluorescence, etc. (mainly absorbs the visible region from the near ultraviolet), blocks or blocks its transmission, decomposes or alters the contents packed in the packaging bag, or discolors, It is intended to prevent photodegradation such as other, and specifically, for example, use one or a mixture of two or more kinds of colorants such as various black-based inorganic or organic dyes and pigments. Is desirable.
In the present invention, examples of colorants such as various black inorganic and organic dyes and pigments include iron black, graphite, or carbon black, and electrically conductive materials (polyaniline, polypyrrole). -1) or 2 or more types of black pigments such as other can be used.
Therefore, in the present invention, the carbon black as the black pigment is a carbon black as a special pigment of benzpyrene free which avoids the incorporation of benzpyrene, which has recently been pointed out to be carcinogenic. Is preferably used.
In the present invention, the black pigment is used in an amount of about 0.1 wt% to 20.0 wt%, preferably 0.3 wt% to 10.0 wt%, relative to the polypropylene resin forming the resin composition. It is desirable to add about%.

  Next, in the present invention, each resin composition constituting the heat-sealable coextruded laminated film having the white layer according to the present invention will be described in more detail. First, in the present invention, the white layer according to the present invention is described. Examples of the resin composition for forming a transparent or translucent resin layer constituting a heat-sealable coextruded laminated film having 1 or more of the above-mentioned polyolefin resins are the main components of the vehicle In addition, if necessary, when forming the film, for example, film processability, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, slipperiness, releasability, difficulty For the purpose of improving and modifying flammability, antifungal properties, electrical characteristics, strength, etc., one or more kinds of various plastic compounding agents and additives are arbitrarily added, and further required. Add solvent, diluent, etc. , And sufficiently kneaded, it is possible to adjust the resin composition for forming a transparent or semi-transparent resin layer according to the present invention.

  Next, in the present invention, as the resin composition for forming the white resin layer constituting the heat-sealable coextruded laminated film having the white layer according to the present invention, for example, one kind of the above-mentioned polyolefin resin Or two or more kinds as a main component of the vehicle, to which one or more of the above white pigments are added, and the content of the above white pigment is 0.5 wt% to 30.0 wt% %, Preferably 5.0% to 20.0% by weight, and if necessary, when forming the film, for example, film processability, heat resistance, weather resistance Various plastics blended for the purpose of improving and modifying properties, mechanical properties, dimensional stability, antioxidant properties, slipperiness, mold release properties, flame retardancy, antifungal properties, electrical properties, strength, etc. 1 or 2 types of additives and additives are optionally added, and If desired, a solvent, adding a diluent or the like, and sufficiently kneaded, it is possible to prepare a resin composition for forming the white resin layer according to the present invention.

  Next, as a resin composition for forming a light-shielding black resin layer constituting the heat-sealable coextruded laminated film having a white layer according to the present invention, for example, one kind of the above-mentioned polyolefin resin Or two or more kinds as a main component of the vehicle, to which one or more kinds of the above black pigments are added, and the content of the above black pigment is 0.1% by weight based on the polyolefin resin. % To about 20.0% by weight, preferably 0.3% to 10.0% by weight, and if necessary, when forming the film, for example, film processability, For the purpose of improving and modifying heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, slipperiness, mold release properties, flame retardancy, antifungal properties, electrical properties, strength, etc. One or more kinds of various plastic compounding agents and additives Was added to the intention, further, if necessary, a solvent, adding a diluent or the like, and sufficiently kneaded, it is possible to prepare a resin composition for forming the resin layer of the black according to the present invention.

  In the present invention, as the resin composition for forming the light-shielding gray resin layer constituting the heat-sealable coextruded laminated film having the white layer according to the present invention, for example, the above-mentioned polyolefin resin 1 or 2 or more of the above are used as the main component of the vehicle, to which 1 or 2 or more of the above black pigments and 1 or 2 or more of the above white pigments are added, and the above black pigment is added. The pigment content is about 0.1% to 20.0% by weight, preferably 0.3% to 10.0% by weight, based on the polyolefin resin. The amount is about 1 to 30 times, preferably about 3 to 15 times the content of the black pigment, and if necessary, when forming the film, for example, , Film processability, heat resistance, weather resistance, mechanical Various plastic additives and additives for the purpose of improving and improving quality, dimensional stability, antioxidant properties, slipperiness, mold release properties, flame retardancy, antifungal properties, electrical properties, strength, etc. A resin composition for forming a gray resin layer according to the present invention is optionally added, and if necessary, a solvent, a diluent and the like are added and kneaded sufficiently. Can be prepared.

  In the present invention, in each resin composition constituting the heat-sealable coextruded laminated film having the white layer according to the present invention, examples of the plastic compounding agent and additives include a lubricant. , Crosslinking agent, antioxidant, ultraviolet absorber, light stabilizer, filler, reinforcing agent, antistatic agent, flame retardant, flame retardant, foaming agent, antifungal agent, pigment, dye, dispersant, surfactant, An anti-blocking agent, etc. can be used, and a modifying resin can also be used. Further, the addition amount can be from a very small amount to several tens of weight% depending on the purpose. And can be optionally added.

Furthermore, in the above, as the compounding agent or additive, specifically, a lubricant having its own lubricity and little migration in the resin can be used. For example, liquid paraffin, white Vaseline, petroleum wax, microcrystalline wax, montan wax, polyethylene wax and the like, higher fatty acids having 8 to 22 carbon atoms, or higher fatty acid aluminum, higher fatty acid calcium, higher fatty acid magnesium higher fatty acid zinc, higher fatty acid lithium Higher fatty acids or metal salts thereof, linear aliphatic monohydric alcohols having 8 to 18 carbon atoms, glycerin, sorbitol, propylene glycol, pentaerythritol, triethylene glycol, etc. Aliphatic alcohols, higher fatty acids having 4 to 22 carbon atoms and straight chain aliphatics having 8 to 18 carbon atoms Esters with polyhydric alcohols, butyl acetyl citrate, di-2-ethyl-hexyl adipate, azelaic acid-n-hexyl, ethanediol montanate, poly (1.3-butanediol adipate) ester, acetylricino Methyl ester, poly (1.3-butylene glycol, 1.4-butylene glycol, octyl alcohol adipate) ester, ester of sugar sugar and fatty acid ester, hydrogenation Edible oils and fats, castor oil, spam acetyl wax, glycerides of acetylated monoglyceride sugar, ethylene bis-fatty acid amide represented by, for example, ethylene bisoleyl amide having 16 to 18 carbon atoms, higher fatty acid amide having 8 to 22 carbon atoms , Stearyl erucamide, erucic acid amide, oleyl palmitoamide, etc. 1 to 2 types of fatty acid amides, and other types such as methylhydrodiene polysiloxane, dimethyl polysiloxane, methylphenyl polysiloxane, silicone oil jarodine such as polyoxyalkylene dimethylpolysiloxane, and glycerin ester of maleic acid modified rosin The above can be used.
In the present invention, among the lubricants as described above, in particular, erucic acid amide, ethylene bis oleyl amide, stearic acid amide, oleic acid amide, methylene bis stearic acid amide, etc. themselves have lubricity, It is a very effective material.
As the addition amount of the above-mentioned lubricant, it is preferable to add at a ratio of about 0.08 wt% to 10.0 wt% with respect to 100 parts by weight of polyolefin resin, barrier resin, or adhesive resin. .

In the present invention, other oxides such as aluminum oxide, magnesium oxide, silica, calcium oxide, titanium oxide, and zinc oxide; hydroxides such as aluminum hydroxide, magnesium hydroxide, and calcium hydroxide; Carbonates such as magnesium and calcium carbonate, sulfates such as calcium sulfate and barium sulfate, silicates such as magnesium silicate, aluminum silicate, calcium silicate and aluminosilicate, and others, kaolin, talc, diatomaceous earth, etc. Anti-blocking agent based on inorganic compounds, or high-density polyethylene, ultra-high molecular weight polyethylene having a molecular weight of 300000 or more, polypropylene, polycarbonate, polyamide, polyester, melamine resin, diallyl phthalate resin, acrylic resin, etc. Organic consisting of fine powder It one free of compounds based antiblocking agents can be added two or more.
The addition amount is preferably about 0.01 to 3% by weight with respect to 100 parts by weight of polyolefin resin, barrier resin, or adhesive resin.

  Next, in the present invention, a method for producing a heat-sealable coextruded laminated film having a white layer according to the present invention using each of the resin compositions as described above will be described. First, each resin composition is prepared as described above, then the resin composition is used, and then the resin composition is used, for example, a T-die co-extruder, an inflation co-extruder, etc. Can be used to produce a heat-sealable coextruded laminated film having a white layer according to the present invention.

  Thus, in the present invention, a specific method for producing a heat-sealable coextruded laminated film having a white layer according to the present invention using each of the resin compositions as described above will be described. First, as described above, a resin composition for forming a transparent or translucent resin layer according to the present invention and a resin composition for forming a white resin layer according to the present invention are prepared, and then Two types of resin compositions are used, and these are co-extruded using, for example, a T-die co-extruder, an inflation co-extruder, etc., and the heat-sealable co-extrusion according to the present invention is used. It consists of a laminated film. Furthermore, the first layer is a transparent or translucent resin layer, the second layer is a white resin layer, and the third layer is a transparent or translucent resin layer in that order. It has a white layer consisting of two types and three layers according to the present invention having a laminated structure. Ruhi - tosylate - can be produced Le of coextruded multilayer films.

  Alternatively, in the present invention, first, as described above, the resin composition for forming the transparent or translucent resin layer according to the present invention, the resin composition for forming the white resin layer according to the present invention, and the present invention A resin composition for forming a light-shielding black or gray resin layer is prepared, and then the three types of resin compositions are used. These are used, for example, as a T-die coextrusion machine or an inflation coextrusion machine. A co-extrusion molding using a machine, etc., comprising the heat-sealable co-extrusion laminated film according to the present invention, wherein the first layer is a transparent or translucent resin layer, and the second layer is white Three types according to the present invention comprising a resin layer, a third layer comprising a light-shielding black or gray resin layer, and a fourth layer co-extrusion laminated in order of a transparent or translucent resin layer. A heat-sealable coextrusion laminated film having a white layer consisting of four layers is manufactured. It can be.

The above examples illustrate one or two examples of the method for producing a heat-sealable coextruded laminated film having a white layer according to the present invention, and the present invention is not limited thereto. Is.
In general, when each of the resin compositions as described above is used to form a heat-sealable coextruded laminated film having a white layer according to the present invention, the film is formed. For example, when replacing (purging) a product, work such as disassembly and cleaning of an extruder or the like is loaded. Therefore, it is desired to avoid using a colorant such as a pigment in the resin composition. It is desired to form an additive-free film.
Therefore, in the present invention, as an outer layer, in order to form a laminated film in which dirt due to the colorant such as pigment does not occur in a die that is most difficult to disassemble, although it is difficult to avoid dirt due to the colorant such as the pigment of the extruder. , Using a resin composition that constitutes a transparent or translucent resin layer to which no colorant such as a pigment is added, whereby the resin film without the addition of a colorant such as a pigment is set to 5 μm to 100 μm. It has the advantage of protecting dirt and the like. Further, in the present invention, when producing a heat-sealable coextruded laminated film having a white layer according to the present invention, a transparent or translucent resin layer, a white resin layer, a light-shielding black or gray resin The layers and the like can be used by dividing each resin composition into two or more resin compositions and co-extrusion lamination not only in one layer but also in two or more layers.
Furthermore, in the present invention, as the heat-sealable coextruded laminated film having a white layer according to the present invention, other materials may be used depending on the purpose of use, use, etc., and this may be arbitrarily coextruded. Thus, a light-shielding coextruded laminated film having various forms can be designed and manufactured.

Next, in the present invention, the film thickness of the heat-sealable coextruded laminated film having a white layer according to the present invention is about 14 μm to 230 μm, preferably about 15 μm to 220 μm.
Thus, in the heat-sealable coextruded laminated film having a white layer according to the present invention, the film thickness of each layer constituting the heat-shearable coextruded laminated film is firstly transparent or semi-transparent. The transparent resin layer has a thickness of 5 μm to 100 μm, preferably about 10 μm to 80 μm, and the white resin layer has a thickness of 4 μm to 30 μm, preferably about 5 μm to 20 μm. Is preferably in the range of about 3 μm to 30 μm, preferably about 5 μm to 20 μm.
In the above, as the film thickness of each layer constituting the heat-sealable coextruded laminated film having a white layer according to the present invention, first, the film thickness of the transparent or translucent resin layer is less than 5 μm. -It is not preferable because it is inferior in the property, and if it exceeds 100 μm, the film thickness becomes high, which is not preferable because it is wasted.
Next, when the thickness of the white resin layer is less than 4 μm, it is difficult to perform its function, and it is not preferable because of its appearance, aesthetics, etc. being reduced. When the thickness exceeds 30 μm, the function is sufficiently achieved, and further, although the light shielding performance and concealing performance are increased, the overall thickness is increased, and there is a possibility that the impact on the environment as packaging waste may increase. It is not preferable for the reason.
Next, when the film thickness of the light-shielding black or gray resin layer is less than 3 μm, the function as a light-shielding or light-shielding layer is deteriorated, and it is greatly influenced by thickness unevenness. It is not preferable because it may cause problems, and if the film thickness exceeds 30 μm, the light shielding property or light shielding property is improved. This is not preferable for reasons such as difficulty.

  In the present invention, in order to improve the laminating strength between layers of each layer constituting the heat-sealable coextruded laminated film having the white layer according to the present invention, the tight adhesion strength, etc., a polyolefin-based adhesive Resin, specifically, for example, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, polyethylene resin or Polyolefin resins such as polypropylene resins are modified with unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic anhydride, fumaric acid, maleic acid, itaconic acid, etc. -One or more kinds of polyolefin resins having tosyl properties can be used.

Next, in the present invention, as a stretched resin film having an inorganic oxide vapor deposition film constituting the boil-retort pouch according to the present invention, this is mainly a barrier property that prevents permeation of oxygen gas, water vapor, etc. The effect of this is achieved.
Thus, in the present invention, as the stretched resin film having the above-described inorganic oxide vapor-deposited film, for example, on one surface of the stretched resin film, chemical vapor deposition, physical vapor deposition, or A stretched resin film having a single-layer film composed of one layer of an inorganic oxide vapor-deposited film, a multilayer film composed of two or more layers, or a composite film formed of two or more layers, and an inorganic oxide vapor-deposited film Can be used.

In the present invention, the inorganic oxide vapor-deposited film by the chemical vapor deposition method will be described in more detail. Examples of the inorganic oxide vapor-deposited film by the chemical vapor deposition method include plasma chemical vapor deposition, thermal A vapor deposition film of an inorganic oxide can be formed using a chemical vapor deposition method (chemical vapor deposition method, CVD method) such as a chemical vapor deposition method or a photochemical vapor deposition method.
In the present invention, specifically, a vapor deposition monomer gas such as an organosilicon compound is used as a raw material on one surface of a stretched resin film, and an inert gas such as argon gas or helium gas is used as a carrier gas. Furthermore, it is possible to form a vapor deposition film of an inorganic oxide such as silicon oxide by using a low temperature plasma chemical vapor deposition method using an oxygen gas or the like as an oxygen supply gas and using a low temperature plasma generator or the like. .
In the above, for example, high-frequency plasma, pulse wave plasma, microwave plasma, or the like can be used as the low-temperature plasma generator. Thus, in the present invention, highly active and stable plasma is obtained. Therefore, it is desirable to use a high-frequency plasma generator.

Specifically, an example of the formation method of the deposited film of the inorganic oxide by the low temperature plasma chemical vapor deposition method will be described as an example. FIG. 9 shows the inorganic oxide deposited by the plasma chemical vapor deposition method. It is a schematic block diagram of the low temperature plasma chemical vapor deposition apparatus which shows the outline | summary about the formation method of a vapor deposition film.
In the present invention, as shown in FIG. 9, the stretched resin film 34 is fed out from the unwinding roll 33 disposed in the vacuum chamber 32 of the plasma chemical vapor deposition apparatus 31, and the stretched resin film 34 is further fed. Is conveyed onto the cooling / electrode drum 36 circumferential surface through the auxiliary roll 35 at a predetermined speed.
Thus, in the present invention, oxygen gas, inert gas, a monomer gas for vapor deposition such as an organosilicon compound, and the like are supplied from the gas supply devices 37 and 38 and the raw material volatilization supply device 39, and the like. The vapor deposition mixed gas composition was introduced into the vacuum chamber 32 through the raw material supply nozzle 40 without adjusting the vapor deposition mixed gas composition, and was conveyed onto the cooling / electrode drum 36 peripheral surface. Then, plasma is generated on one surface of the stretched resin film 34 by the glow discharge plasma 41 and irradiated to form a vapor-deposited film of an inorganic oxide such as silicon oxide.
In the present invention, at that time, the cooling / electrode drum 36 is applied with a predetermined power from a power source 42 disposed outside the vacuum chamber 32, and is also in the vicinity of the cooling / electrode drum 36. The generation of plasma is promoted by arranging the magnet 43.
Next, after forming a vapor deposition film of an inorganic oxide such as silicon oxide on one surface of the stretched resin film 34 as described above, the stretched resin film 34 is supported in a state where the vapor deposition film of the inorganic oxide is held. -It can wind up on the winding roll 45 via the roll 44, and can form the vapor deposition film | membrane of the inorganic oxide by the plasma chemical vapor deposition method concerning this invention.
In the figure, 46 represents a vacuum pump.
The above exemplification is an example, and it goes without saying that the present invention is not limited thereby.
Although not shown, in the present invention, the inorganic oxide vapor deposition film may be not only one layer of the inorganic oxide vapor deposition film but also a multilayer film in which two or more layers are laminated, and is used. The materials may be used alone or as a mixture of two or more, and an inorganic oxide vapor deposition film mixed with different materials may be formed.

In the above, the inside of the vacuum chamber is depressurized by a vacuum pump and adjusted to a vacuum degree of 1 × 10 ⁻¹ to 1 × 10 ⁻⁸ Torr, preferably a vacuum degree of 1 × 10 ⁻³ to 1 × 10 ⁻⁷ Torr. It is desirable to do.
In the raw material volatilization supply device, the organic silicon compound as the raw material is volatilized and mixed with oxygen gas, inert gas, etc. supplied from the gas supply device, and this mixed gas is supplied to the vacuum chamber through the raw material supply nozzle. It is introduced in the inside.
In this case, the content of the organosilicon compound in the mixed gas is about 1 to 40%, the content of oxygen gas is about 10 to 70%, and the content of inert gas is about 10 to 60%. For example, the mixing ratio of the organosilicon compound, oxygen gas, and inert gas can be about 1: 6: 5 to 1:17:14.
On the other hand, since a predetermined voltage is applied to the cooling / electrode drum from the power source, glow discharge plasma is generated in the vicinity of the opening of the raw material supply nozzle in the vacuum chamber and the cooling / electrode drum. The glow discharge plasma is derived from one or more gas components in the mixed gas. In this state, the stretched resin film is transported at a constant speed, and the glow discharge plasma is used to cool the electrode drum peripheral surface. A vapor-deposited film of an inorganic oxide such as silicon oxide can be formed on the surface of the upper stretched resin film.
At this time, the degree of vacuum in the vacuum chamber should be adjusted to 1 × 10 ⁻¹ to 1 × 10 ⁻⁴ Torr, preferably 1 × 10 ⁻¹ to 1 × 10 ⁻² Torr. In addition, it is desirable that the stretched resin film has a conveying speed of about 10 to 300 m / min, preferably about 50 to 150 m / min.

In addition, in the plasma chemical vapor deposition apparatus described above, an inorganic oxide vapor deposition film such as silicon oxide is formed on one surface of the stretched resin film by oxidizing the plasma source gas with oxygen gas while oxidizing SiO _x . Therefore, the formed deposited film of inorganic oxide such as silicon oxide is a dense, flexible, continuous layer with few gaps. The barrier property of the deposited film of inorganic oxide such as silicon oxide is much higher than that of the deposited film of inorganic oxide such as silicon oxide formed by the conventional vacuum deposition method. It is possible to obtain sex.
In the present invention, the surface of the stretched resin film is cleaned by the SiO _x plasma, and polar groups, free radicals, etc. are generated on the surface of the stretched resin film. It has the advantage that the tight adhesion between the vapor deposition film of the product and the surface of the stretched resin film is high.
Furthermore, as described above, the degree of vacuum when forming a continuous film of an inorganic oxide such as silicon oxide is about 1 × 10 ⁻¹ to 1 × 10 ⁻⁴ Torr, preferably 1 × 10 ⁻¹ to 1 × 10. ^{-2 Since} it is prepared at the Torr position, the degree of vacuum when forming a deposited film of an inorganic oxide such as silicon oxide by the conventional vacuum evaporation method is compared with the 1 × 10 ⁻⁴ to 1 × 10 ⁻⁵ Torr position. Since the degree of vacuum is low, it is possible to shorten the vacuum state setting time when the stretched resin film is exchanged, and it is easy to stabilize the degree of vacuum and the film forming process is stabilized.

In the present invention, a deposited film of silicon oxide formed using a vapor-deposited monomer gas such as an organosilicon compound chemically reacts with a vapor-deposited monomer gas such as an organosilicon compound and oxygen gas. Is closely bonded to one surface of the stretched resin film to form a dense, flexible thin film, and is generally represented by the general formula SiO _x (where X represents a number from 0 to 2). Is a continuous thin film mainly composed of silicon oxide.
Thus, the silicon oxide vapor-deposited film is represented by the general formula SiO _x (where X represents a number from 1.3 to 1.9) from the viewpoint of transparency and barrier properties. A thin film mainly composed of a deposited silicon oxide film is preferable.
In the above, the value of X varies depending on the molar ratio of the vapor-deposited monomer gas and oxygen gas, the energy of the plasma, etc. Generally, the gas permeability decreases as the value of X decreases, but the film itself Becomes yellowish and the transparency is poor.

In addition, the silicon oxide vapor-deposited film is mainly composed of silicon oxide, and further, at least one kind of compound composed of one kind of carbon, hydrogen, silicon, or oxygen, or two or more kinds thereof is chemically used. It consists of the vapor deposition film | membrane contained by a coupling | bonding etc., It is characterized by the above-mentioned.
For example, when a compound having a C—H bond, a compound having a Si—H bond, or a carbon unit is in the form of graphite, diamond, fullerene, etc. A derivative may be contained by a chemical bond or the like.
Specific examples include hydrocarbons having a CH ₃ site, hydrosilica such as SiH ₃ silyl, SiH ₂ silylene, and hydroxyl derivatives such as SiH ₂ OH silanol.
In addition to the above, the type, amount, etc., of the compound contained in the deposited film of silicon oxide can be changed by changing the conditions of the vapor deposition process.
Thus, the content of the above compound in the deposited film of silicon oxide is about 0.1 to 50%, preferably about 5 to 20%.
In the above, if the content is less than 0.1%, the impact resistance, spreadability, flexibility, etc. of the deposited silicon oxide film become insufficient, and scratches, cracks, etc. are likely to occur due to bending. It is difficult to stably maintain a high barrier property, and if it exceeds 50%, the barrier property is lowered, which is not preferable.
Furthermore, in the present invention, in the silicon oxide vapor deposition film, the content of the above-mentioned compound is preferably decreased from the surface of the silicon oxide vapor deposition film in the depth direction. On the surface, the impact resistance and the like can be enhanced by the above compound and the like. On the other hand, since the content of the above compound is small at the interface with the surface of the stretched resin film, the stretched resin film and silicon oxide are deposited. It has the advantage that the tight adhesion with the film becomes strong.

Thus, in the present invention, the above silicon oxide vapor deposition film is subjected to surface analysis such as an X-ray photoelectron spectrometer (Xray Photoelectron Spectroscopy, XPS), a secondary ion mass spectrometer (Secondary Ion Mass Spectroscopy, SIMS), etc. The physical properties as described above can be confirmed by conducting an elemental analysis of the deposited film of silicon oxide using a method of analyzing by ion etching in the depth direction using an apparatus.
In the present invention, the film thickness of the above-described silicon oxide vapor deposition film is preferably about 50 to 4000 mm, and specifically, the film thickness is preferably about 100 to 1000 mm. In the above, if it is thicker than 1000 mm, and more preferably 4000 mm, it is not preferable because cracks and the like are likely to occur in the film, and if it is less than 100 mm, further less than 50 mm, there is an effect of barrier properties. Is not preferable because it becomes difficult.
In the above, the film thickness can be measured by a fundamental parameter method using, for example, a fluorescent X-ray analyzer (model name, RIX2000 type) manufactured by Rigaku Corporation. In the above, as means for changing the film thickness of the silicon oxide vapor deposition film, the volume velocity of the vapor deposition film is increased, that is, the method of increasing the amount of monomer gas and oxygen gas and the vapor deposition rate. This can be done by a method of slowing down.

Next, in the above, as a vapor deposition monomer gas such as an organic silicon compound that forms a vapor deposition film of an inorganic oxide such as silicon oxide, for example, 1.1.3.3-tetramethyldisiloxane, hexamethyldisiloxane Siloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyl Trimethoxysilane, methyltriethoxysilane, octamethylcyclotetrasiloxane, etc. can be used.
In the present invention, among the organic silicon compounds as described above, the use of 1.1.3.3-tetramethyldisiloxane or hexamethyldisiloxane as a raw material is easy to handle and formed continuous film. In view of the above characteristics and the like, it is a particularly preferable raw material.
Moreover, in the above, as an inert gas, argon gas, helium gas, etc. can be used, for example.

Next, in the present invention, the inorganic oxide vapor-deposited film by the physical vapor deposition method will be described in more detail. Examples of the inorganic oxide vapor-deposited film by the physical vapor deposition method include, for example, vacuum vapor deposition and sputtering. A vapor deposition film of an inorganic oxide can be formed using a physical vapor deposition method (Physical Vapor Deposition method, PVD method) such as a method, an ion plating method, or an ion cluster beam method.
In the present invention, specifically, a metal or a metal oxide is used as a raw material, this is heated and vaporized, and this is vapor-deposited on one surface of the stretched resin film, or a metal or metal as a raw material. An oxidation reaction deposition method that uses metal oxide, oxidizes by introducing oxygen and deposits on one side of the stretched resin film, and a plasma-assisted oxidation reaction deposition method that further assists the oxidation reaction with plasma. It can be used to form a deposited film.
In the above, as a heating method for the vapor deposition material, for example, a resistance heating method, a high frequency induction heating method, an electron beam heating method (EB), or the like can be used.

In the present invention, a specific example of a method for forming a thin film of an inorganic oxide by physical vapor deposition will be described. FIG. 10 is a schematic configuration diagram showing an example of a take-up vacuum deposition apparatus.
As shown in FIG. 10, the stretched resin film 54 fed out from the unwinding roll 53 in the vacuum chamber 52 of the wind-up type vacuum vapor deposition apparatus 51 is cooled through the guide rolls 55, 56 and the like. Guided to the coated drum 57.
Thus, on one surface of the stretched resin film 54 guided on the cooled coating drum 57, a vapor deposition source 59 heated by the crucible 58, for example, metal aluminum or aluminum oxide is provided. Further, if necessary, an oxygen gas or the like is ejected from the oxygen gas outlet 60, and an inorganic oxide vapor deposition film such as aluminum oxide is formed through the masks 61 and 61 while supplying this. Next, in the above, for example, in the above, the stretched resin film 54 on which an inorganic oxide vapor deposition film such as aluminum oxide is formed is sent out through the guide rollers 62 and 63 and wound up on the winding roller 64. Thus, an inorganic oxide vapor-deposited film can be formed by the physical vapor deposition method according to the present invention.
In the present invention, the first-layer inorganic oxide vapor deposition film is first formed using the above-described take-up vacuum vapor deposition apparatus, and then the inorganic oxide vapor deposition film is formed in the same manner. Further, an inorganic oxide vapor deposition film is formed on the substrate, or by using the above-described take-up vacuum vapor deposition apparatus, these are connected in series, and the inorganic oxide vapor deposition is continuously performed. By forming the film, it is possible to form a vapor-deposited film of an inorganic oxide composed of two or more multilayer films.

In the above, as the inorganic oxide vapor-deposited film, basically, any thin film obtained by vapor-depositing a metal oxide can be used. For example, silicon (Si), aluminum (Al), magnesium (Mg), Metal oxides such as calcium (Ca), potassium (K), tin (Sn), sodium (Na), boron (B), titanium (Ti), lead (Pb), zirconium (Zr), yttrium (Y) The deposited film can be used.
Thus, preferable examples include vapor-deposited films of metal oxides such as silicon (Si) and aluminum (Al).
Also, deposited film of oxides of the above metals, silicon oxides, aluminum oxides, can be referred to as a metal oxide like such as magnesium oxide, the notation is, for example, SiO _X, AlO _X, MgO MO _X (in the formula, M represents a metal element, the value of X is in the range respectively of a metal element different.) as _X, etc. represented by.
As the range of the value of X, 0 to 2 for silicon (Si), 0 to 1.5 for aluminum (Al), 0 to 1 for magnesium (Mg), 0 to 1 for calcium (Ca). 1, 0 to 0.5 for potassium (K), 0 to 2 for tin (Sn), 0 to 0.5 for sodium (Na), 0 to 1, 5 for boron (B), titanium ( Ti) can be 0 to 2, lead (Pb) is 0 to 1, zirconium (Zr) is 0 to 2, and yttrium (Y) is 0 to 1.5.
In the above, when X = 0, it is a complete metal and is not transparent and cannot be used at all. The upper limit of the range of X is a completely oxidized value.
In the present invention, generally, examples other than silicon (Si) and aluminum (Al) are scarce, silicon (Si) is 1.0 to 2.0, and aluminum (Al) is 0.5. Those with values in the range of -1.5 can be used.
In the present invention, the film thickness of the inorganic oxide vapor-deposited film as described above varies depending on the metal used or the type of metal oxide, but is, for example, about 50 to 2000 mm, preferably 100 to 1000 mm. It is desirable to select and form arbitrarily within the range.
Moreover, in this invention, as a vapor deposition film of an inorganic oxide, as a metal or metal oxide to be used, it is used by 1 type, or 2 or more types of mixtures, and vapor deposition of the inorganic oxide mixed by the dissimilar material A membrane can also be constructed.

By the way, in the present invention, the surface of the inorganic oxide vapor deposition film provided on one surface of the stretched resin film as described above, for example, with a primer agent layer, a printed pattern layer, an intermediate substrate, and the like It is preferable to form a plasma-treated surface with oxygen gas in order to improve the tight adhesion and eventually tightly adhere both of them and prevent the occurrence of delamination, etc. It is.
Thus, in the present invention, as the plasma treatment surface with oxygen gas, using a plasma surface treatment method or the like for performing surface modification using a plasma gas generated by ionizing gas by arc discharge, It is possible to form a plasma treated surface with oxygen gas.
Thus, in the present invention, the plasma gas is plasma surface treatment using oxygen gas or a mixed gas of oxygen gas and nitrogen gas, argon gas, helium gas, or other inert gas. By performing the treatment, a plasma treatment surface with oxygen gas can be formed.
In the present invention, when a plasma-treated surface with oxygen gas is formed, an inorganic oxide vapor-deposited film is formed, and immediately thereafter, the inorganic oxide vapor-deposited film is subjected to plasma discharge treatment with oxygen gas in-line. By doing so, a plasma-treated surface with oxygen gas can be formed.
Further, in the present invention, it is preferable to perform the plasma discharge treatment in consideration of conditions such as plasma output, plasma gas type, plasma gas supply amount, treatment time, and the like.
In the present invention, as a method for generating plasma, for example, a direct current glow discharge, a high frequency discharge, a microwave discharge, or the like can be used.
Of course, in the present invention, the plasma processing surface can be formed also by the atmospheric pressure plasma processing method.

Next, in the present invention, a stretched resin film constituting a stretched resin film having an inorganic oxide vapor deposition film will be described. As such a stretched resin film, this is the same as the stretched substrate film described above. Because it is a basic material or auxiliary material that constitutes a boil / retort pouch according to the above, and it is a base material that holds an inorganic oxide vapor-deposited film, it must first withstand the conditions of formation, processing, etc. In addition, they can be held well without impairing their characteristics, and further, in the process of laminating laminated materials, making bags for packaging, etc., workability, heat resistance, slipperiness, pin resistance It is possible to use a stretched resin film or sheet that is excellent in various physical properties such as the properties and the like, and that can satisfy other conditions.
In the present invention, specific examples of the resin film or sheet include polyolefin resins such as polyethylene resins and polypropylene resins, cyclic polyolefin resins, polystyrene resins, acrylonitrile-styrene copolymer. Polyester such as coalescence (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), poly (meth) acrylic resin, polycarbonate resin, polyethylene terephthalate, polyethylene naphthalate Various stretched resin films or sheets such as polyamide resins, polyamide resins such as various nylon resins, polyurethane resins, acetal resins, cellulose resins, and the like can be used.
In the present invention, it is particularly preferable to use a polyester resin, a polyolefin resin, or a polyamide resin film or sheet among the above-described resin films or sheets.

In the present invention, as the above-mentioned various resin films or sheets, for example, one or more of the above-mentioned various resins are used, and an extrusion method, a cast molding method, a T-die method, a cutting method, an inflation method are used. -A method of forming the above-mentioned various resins independently using a film-forming method such as an ionization method or the like, or a method of forming a multilayer co-extrusion film using two or more types of various resins Furthermore, by using two or more kinds of resins, various resin films or sheets are manufactured by a method of forming a film by mixing before forming a film, and further, for example, a tenter method Alternatively, it is possible to use various resin films or sheets that are stretched in a uniaxial or biaxial direction using a tuber system or the like.
In the present invention, the film thickness of various resin films or sheets is preferably about 6 to 200 μm, more preferably about 9 to 100 μm.

In addition, when using one or more of the above-mentioned various resins and forming the film, for example, film processability, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, slipperiness Various plastic compounding agents and additives can be added for the purpose of improving and modifying mold release properties, flame retardancy, antifungal properties, electrical properties, strength, etc. Can be arbitrarily added from a very small amount to several tens of percent depending on the purpose.
In the above, as a general additive, for example, a lubricant, a crosslinking agent, an antioxidant, an ultraviolet absorber, a light stabilizer, a filler, a reinforcing agent, an antistatic agent, a pigment, and the like can be used. Furthermore, a modifying resin or the like can be used.

In the present invention, the surface of the above-mentioned various resin films or sheets may have a desired surface in advance, if necessary, in order to improve the close adhesion with the vapor-deposited film of the inorganic oxide. A treatment layer can be provided.
In the present invention, as the surface treatment layer, for example, corona discharge treatment, ozone treatment, low temperature plasma treatment using oxygen gas or nitrogen gas, glow discharge treatment, oxidation treatment using chemicals, etc., For example, a corona treatment layer, an ozone treatment layer, a plasma treatment layer, an oxidation treatment layer, or the like can be formed by providing a pretreatment such as others arbitrarily.
The surface pretreatment is carried out as a method for improving the close adhesion between various resin films or sheets and an inorganic oxide vapor deposition film described later. In addition, for example, a primer coat agent layer, an undercoat agent layer, an anchor coat agent layer, adhesion on the surface of various resin films or sheets in advance. An agent layer, a deposition anchor coat agent layer, or the like can be arbitrarily formed to form a surface treatment layer.
Examples of the pretreatment coating agent layer include, for example, polyester resins, polyamide resins, polyurethane resins, epoxy resins, phenol resins, (meth) acrylic resins, polyvinyl acetate resins, A resin composition containing a polyolefin resin such as polyethylene or polypropylene, or a copolymer or modified resin thereof, a cellulose resin, or the like as a main component of the vehicle can be used.

In the present invention, since the packaging container is usually subjected to severe physical and chemical conditions, the packaging material constituting the packaging container is required to have strict packaging suitability and deformation. Various conditions such as prevention strength, drop impact strength, pinhole resistance, heat resistance, sealability, quality maintenance, workability, hygiene, and the like are required. Other materials satisfying such various conditions can be arbitrarily selected, and these can be arbitrarily laminated together with the above materials to produce laminated materials having various layer configurations.
Specifically, for example, low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-acrylic acid Ethyl copolymer, ethylene-acrylic acid or methacrylic acid copolymer, methylpentene polymer, polybutene resin, polyvinyl chloride resin, polyvinyl acetate resin, polyvinylidene chloride resin, vinyl chloride-vinylidene chloride copolymer Polymer, poly (meth) acrylic resin, polyacrylonitrile resin, polystyrene resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), polyester resin, Polyamide resin, polycarbonate Known resins such as neat resins, polyvinyl alcohol resins, saponified ethylene-vinyl acetate copolymers, fluorine resins, diene resins, polyacetal resins, polyurethane resins, nitrocellulose, etc. Any resin film or sheet can be selected and used.
In addition, for example, a film such as cellophane, synthetic paper, and the like can be used.
In the present invention, the above-described film or sheet may be any of unstretched, uniaxially or biaxially stretched.
The thickness is arbitrary, but can be selected from a range of several μm to 300 μm.
Furthermore, in the present invention, the film or sheet may be a film having any property such as extrusion film formation, inflation film formation, and coating film.

  Next, in the present invention, as a method for producing a laminated material constituting the above-described boil / retort pouch according to the present invention, for example, a dry laminating layered via a primer agent layer or a laminating adhesive layer, etc. -Manufacture of laminates of various forms using laminate method such as laminate lamination method, extrusion laminating lamination method through primer agent layer or anchor coat agent layer, etc. can do.

The laminating adhesive layer will be described. Examples of the laminating adhesive constituting the laminating adhesive layer include polyvinyl acetate adhesive, ethyl acrylate, butyl, 2 -Homopolymers such as ethylhexyl ester, or polyacrylic acid ester adhesives, such as copolymers thereof with methyl methacrylate, acrylonitrile, styrene, etc., cyanoacrylate adhesives, ethylene and vinyl acetate, acrylic acid Ethylene copolymer adhesives, such as copolymers with monomers such as ethyl, acrylic acid, methacrylic acid, cellulose adhesives, polyester adhesives, polyamide adhesives, polyimide adhesives, urea resins Or an amino resin adhesive made of melamine resin, phenol resin adhesive, epoxy adhesive, Urethane adhesive, reactive (meth) acrylic adhesive, chloroprene rubber, nitrile rubber, rubber adhesive made of styrene-butadiene rubber, silicone adhesive, alkali metal silicate, low melting point glass, etc. It is possible to use an inorganic adhesive made of or other adhesive.
The composition system of the above-mentioned adhesive may be any composition form such as an aqueous type, a solution type, an emulsion type, and a dispersion type, and the properties thereof are film / sheet type, powder type, solid type, etc. Any form may be used, and the adhesion mechanism may be any form such as a chemical reaction type, a solvent volatilization type, a heat melting type, and a hot pressure type.
Thus, the above adhesive can be applied by, for example, a roll coating method, a gravure roll coating method, a kiss coating method, a coating method or the like, or a printing method. The coating amount is preferably about 0.1 to 10 g / m ² (dry state).

The anchor coat agent layer will be described. As an anchor coat agent constituting such an anchor coat agent layer, for example, an organic titanium type such as an alkyl titanate, an isocyanate type, etc. Various aqueous or oil-based anchor coating agents such as polyethyleneimine, polyptadiene, and the like can be used.
The above-mentioned anchor coating agent can be coated using a coating method such as a roll coat, a gravure roll coat, a kiss coat, and the like. The amount is preferably about 0.1 to 5 g / m ² (dry state).

Furthermore, examples of the melt-extruded resin layer in the above-described extrusion lamination method include, for example, polyethylene resins, polypropylene resins, acid-modified polyethylene resins, acid-modified polypropylene resins, ethylene-acrylic acid or methacrylic acid copolymers. , Thermoplastic resins such as styrene resin, ethylene-vinyl acetate copolymer, polyvinyl acetate resin, ethylene-acrylic acid ester or methacrylic acid ester copolymer, polystyrene resin, polyvinyl chloride resin, etc. 1 type, or 2 or more types can be used.
In the extrusion laminating method described above, in order to obtain stronger adhesive strength, for example, lamination can be performed via an anchor coating agent layer such as the above-described anchor coating agent. .

In the present invention, as the primer agent layer, for example, polyurethane resin, polyester resin, polyamide resin, epoxy resin, phenol resin, (meth) acrylic resin, polyvinyl acetate resin, The primer layer can be formed by using a resin composition containing a polyolefin resin such as polyethylene or polypropylene or a copolymer or modified resin thereof, a cellulose resin, or the like as a main component of the vehicle.
In the present invention, for example, a primer coating layer is formed by coating using a coating method such as a roll coat, a gravure roll coat, a kiss coat, or the like. Therefore, the coating amount is preferably about 0.1 to 10 g / m ² (dry state).
Moreover, in this invention, when performing said lamination | stacking, if necessary, pre-treatments, such as a corona treatment and an ozone treatment, can be given to a film.

In the present invention, in the laminated material according to the present invention, an arbitrary printed pattern layer can be provided on the front surface, the back surface, or both surfaces of any material constituting the laminated material.
Thus, in the present invention, as the printed pattern layer, for example, a desired printed pattern made of, for example, characters, figures, symbols, patterns, etc. is printed on the desired material. A printed pattern layer can be formed.
Thus, as the above-mentioned printed pattern layer, specifically, first of all, an ink vehicle consisting of one or more resins such as a resin is used as a main component, and if necessary, a plasticizer and a stabilizer. , Optionally adding one or more additives such as antioxidants, light stabilizers, ultraviolet absorbers, curing agents, crosslinking agents, lubricants, antistatic agents, fillers, etc. A colorant such as a pigment is added, and the ink composition is prepared by sufficiently kneading with a solvent, a diluent, etc., and then the ink composition is used, for example, gravure printing, offset printing, letterpress printing, screen printing The printing method such as character printing, transfer printing, flexographic printing, etc. is used to print a desired printing pattern consisting of characters, figures, symbols, patterns, etc. on the above desired material. The printed pattern layer can be formed.

  In the above, as the vehicle for ink, known ones such as sesame oil, drill oil, soybean oil, hydrocarbon oil, rosin, rosin ester, rosin modified resin, shellac, alkyd resin, phenol resin, malein Acid resins, natural resins, hydrocarbon resins, polyvinyl chloride resins, polyvinyl acetate resins, polystyrene resins, polyvinyl butyral resins, acrylic or methacrylic resins, polyamide resins, polyester resins, polyurethane resins Use one or more of epoxy resin, urea resin, melamine resin, amino alkyd resin, phenol resin, nitrocellulose, ethylcellulose, chlorinated rubber, cyclized rubber, etc. Can do.

Thus, in the present invention, a method for making a packaging bag according to the present invention using the laminated material according to the present invention as described above will be described. Use the inner layer of heat-seal resin film facing each other and fold it up, or wrap the two sheets together, and heat-seal the peripheral edge. -The bag part can be provided and a bag for packaging which consists of various forms can be made.
Thus, as a bag-making method, the above-mentioned laminated material is folded with the inner layer faces facing each other, or the two sheets are overlapped, and the peripheral edge of the outer periphery is, for example, a side sheet. Seal type, two-sided seal type, three-sided seal type, four-sided seal type, envelope-sealed seal type, jointed seal type (pillar seal type), pleated seal type It is possible to manufacture various types of packaging bags according to the present invention by heat sealing in the form of a heat seal such as a flat bottom seal type, a square bottom seal type, or the like.
In addition, for example, a self-supporting packaging bag (standing pouch) or the like can be manufactured, and in the present invention, a tube container or the like can also be manufactured using the above-described laminated material.
In the above, as the heat seal method, for example, a bar seal, a rotary roll seal, a belt seal, an impulse seal, a high frequency seal, an ultrasonic seal and the like are known. It can be done by the method.
In the present invention, a spout such as a one-piece type, a two-piece type, or the like, or a zipper for opening and closing can be arbitrarily attached to the packaging bag as described above.

Next, in the present invention, the contents are filled from the opening of the packaging bag produced above, and then the opening is sealed at the upper end with a heat seal or the like.・ Manufacturing a semifinished packaging product using a retort pouch, and then subjecting the semifinished packaging product to a heat sterilization treatment such as a retort treatment or a boil treatment, thereby using the boil / retort pouch according to the present invention. A boiled retort-processed packaged food can be produced.
In the above, as a method for retorting or boiling, for example, a normal retort kettle is used, and the temperature is about 110 to 130 ° C., preferably about 120 ° C., pressure, 1 to 3 kgf / cm ² · G, Preferably, a method of heating and pressurizing at about 2.1 kgf / cm ² · G, about 20 to 60 minutes, preferably about 30 minutes, or temperature, 90 to 100 ° C., preferably 90 ° C. It can be carried out by a method of performing a boil treatment in about front and rear, time, about 5 to 20 minutes, preferably about 10 minutes.
Thus, in the present invention, the contents can be subjected to heat sterilization, heat sterilization cooking, or the like by retort processing or boil processing as described above.

Next, in the present invention, the contents to be filled and packaged in the packaging bag constituting the boil / retort pouch according to the present invention include, for example, cooked food, marine product, frozen food, boiled food, rice cake, liquid soup Various foods and drinks such as sushi, seasonings, drinking water, etc., specifically, for example, curry, stew, soup, meat sauce, hamburger, meatball, sparrow And various foods and beverages such as fluid foods such as oden and porridge, jelly-like foods, seasonings, water and others.
Thus, in the present invention, the boil-retort pouch according to the present invention is a heat-sealable co-extruded laminated film in which a pigment or the like in a food or drink packed and packaged during the boil-retort treatment has a white layer. And the pigment dyes a heat-sealable co-extruded laminated film having a white layer, and is the outside of the packaging bag and has a see-through portion of a stretched base film having a see-through portion When seeing through, it is possible to easily visually recognize the dyed state, whereby the presence or absence of heat sterilization treatment such as boil treatment or retort treatment can be confirmed and judged accurately and simply.
In the present invention, the boil / retort pouch according to the present invention is excellent in various physical properties such as heat resistance, pressure resistance, water resistance, heat seal resistance, pin hole resistance, puncture resistance, and the like. In particular, it has excellent barrier properties, transparency, etc. that prevent the permeation of oxygen gas, water vapor, etc., and withstands heat treatment associated with processing such as retort treatment, and further reduces the weight and weight of containers and packaging waste. In addition, the manufacturing cost can be reduced by shortening the manufacturing process, and the contents can be packed and packaged and the quality is excellent.

Furthermore, in the present invention, when the boil / retort pouch according to the present invention has a light-shielding black or gray resin layer in the laminate constituting the stretched resin, it further has an inorganic oxide vapor deposition film. In the case of having a film, etc., it is particularly excellent in light blocking properties, light blocking properties, barrier properties, etc., for example, blocking the transmission of sunlight or fluorescence by the sun or fluorescent lamps, etc., and the contents are decomposed or altered. Or, since it is possible to prevent light degradation such as amber and others, for example, in the case of foods and drinks containing fats and oils as contents, it is due to transmission of sunlight or fluorescence This has the advantage of preventing oxidation of the oil and fat component.
In particular, frozen foods and drinks are usually handled by supermarkets and other mass retailers. In this case, they are sold on display shelves that receive a lot of fluorescence from fluorescent lamps. It's real.
Thus, in frozen foods and beverages sold in the environment as described above, the fat and oil component is greatly affected by light having a wavelength of 500 nm or less, and has a maximum absorption of visible light in the yellow band around 550 nm. Therefore, there is a risk that the oxidation reaction is accelerated by the influence of fluorescence or the like by a fluorescent lamp or the like, and the content is decomposed or altered.

However, in the present invention, in particular, it is excellent in light-shielding property or light-shielding property, for example, blocking the transmission of sunlight or fluorescence by the sun or fluorescent lamp, etc., and the content is decomposed or altered, or is amber, Since it is possible to prevent light deterioration such as other, it is possible to prevent the use of the laminated material according to the present invention, and the frozen food and drink using the packaging bag according to the present invention formed from the laminated material. Is sold in a display shelf that receives a lot of fluorescent light from fluorescent lamps, etc., and even if it is affected by fluorescent light, etc. The reaction can be prevented from being accelerated, and the contents can be prevented from being decomposed or altered.
In the present invention, since the packaged product manufactured above does not use an aluminum foil or an aluminum deposited film, a metal (foreign matter) detector is used, and a metal (foreign matter) is detected by a metal (foreign matter) detector. It has the advantage that detection is also possible.
Next, the present invention will be described more specifically with reference to examples.

(1). First, the following resin compositions (a), (b), and (c) were prepared.
(I). Resin composition constituting the first layer Functional polypropylene block copolymer (manufactured by Sun Aroma Co., Ltd., trade name, PC380A, density = 0.9 g / cm ³ , melt flow rate, MFR = 1.0 g / 10 min) 100 parts by weight, 0.5 parts by weight of synthetic silica, 0.05 parts by weight of erucic acid amide, and 0.05 parts by weight of ethylenebisoleic acid amide were sufficiently kneaded to prepare a resin composition.
(B). Resin composition constituting second layer Functional polypropylene block copolymer (trade name, PC380A, density = 0.9 g / cm ³ , melt flow rate, MFR = 1.0 g / 10 min, manufactured by Sun Aroma Co., Ltd.) 80.0 parts by weight and 20.0 parts by weight of titanium oxide as a white pigment were sufficiently kneaded to prepare a resin composition.
(C). Resin composition constituting third layer Functional polypropylene block copolymer (trade name, PC380A, density = 0.9 g / cm ³ , melt flow rate, MFR = 1.0 g / 10 min, manufactured by Sun Aroma Co., Ltd.) 100 parts by weight, 0.5 parts by weight of synthetic silica, 0.05 parts by weight of erucic acid amide, and 0.05 parts by weight of ethylene bisoleic acid amide were sufficiently kneaded to prepare a resin composition.
Next, using each resin composition prepared above, using a three-type three-layer top-blown air-cooled inflation co-extrusion film forming machine, the layer of the resin composition of (A) is 10 μm, (B) A layer made of the resin composition of 20 μm and (c) a layer of the resin composition of 40 μm were coextruded to form a film of 3 types and 3 layers of coextruded inflation film with a total thickness of 70 μm. A heat sealable coextruded laminated film having a white layer according to the present invention was produced.
(2). On the other hand, a biaxially stretched nylon 6 film having a thickness of 15 μm is used as the stretched resin film, which is mounted on the unwinding roll of the plasma chemical vapor deposition apparatus, and then transported at a line speed of 100 mm / min. A sputtering apparatus is used to introduce an argon gas of 600 sccm, and a plasma treatment is performed at an output of 20 kW to form a plasma treatment surface with an inert gas. Then, the thickness of the plasma treatment surface is reduced under the following conditions. A 200-nm silicon oxide vapor deposition film was formed.
(Deposition conditions)
Reaction gas mixing ratio: Hexamethyldisiloxane: Oxygen gas: Helium = 1: 11: 10 (Unit: Slm)
Ultimate pressure: 5.2 × 10 ⁻⁶ mbar
Film ^- forming pressure: 5.1 × 10 ⁻² mbar
Line speed: 100 m / min
Power: 30kW
Next, immediately after forming the silicon oxide vapor deposition film having a thickness of 200 mm as described above, a glow discharge plasma generator is used on the silicon oxide vapor deposition film surface, and the power is 9 kW, oxygen gas (O ₂ ): argon gas. (Ar) = 7.0: 2.5 (unit: Slm) is used, and oxygen / argon mixed gas plasma treatment is performed at a mixed gas pressure of 6 × 10 ⁻² mbar and a processing speed of 100 m / min. A biaxially stretched nylon 6 film having a silicon oxide vapor deposition film was produced by forming a plasma treated surface in which the surface tension of the vapor deposition film surface of silicon oxide was improved by 54 dyne / cm or more.
(3). Next, a desired printed pattern is formed on the corona-treated surface of a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm except for a non-printed area having a round hole shape with a diameter of 10 mm. On the surface, a two-component curable urethane-based adhesive (main agent: polyester polyol, curing agent: aliphatic socyanate) is used, and the thickness is 4.0 g / m using a gravure roll coating method. ² (Dry) coating to form an adhesive layer for laminating, and then biaxial stretching having the deposited silicon oxide film produced in (2) above on the surface of the laminating adhesive layer Nylon 6 films were laminated with their silicon oxide vapor-deposited surfaces facing each other, and then both were laminated by dry lamination.
Further, on the corona-treated surface of the biaxially stretched nylon 6 film having the vapor-deposited silicon oxide film laminated by dry lamination as described above, a two-component curable urethane adhesive ( Main ingredient: Polyester polyol, Curing agent: Aliphatic socyanate), and apply this to a thickness of 4.0 g / m ² (dry) using a gravure roll coat method for laminating An adhesive layer is formed, and then the heat-sealable coextruded laminated film having the white layer produced in (1) above is applied to the surface of the laminating adhesive layer, the resin of (a) The layer surfaces of the composition were overlapped with each other facing each other, and then both were laminated by dry lamination to produce a laminate according to the present invention.
(4). Next, two sheets of the laminated material manufactured as described above are prepared, and the heat-sealable coextruded laminated film faces are overlapped with each other, and then the outer periphery of the laminated material is formed using an impulse sealer. A three-sided seal-type flexible packaging bag having an opening at the top while forming a seal portion by three-side heat sealing the peripheral edge portion was used as a curry retort pouch.
In the three-sided seal type soft packaging bag manufactured above, the curry is filled and packaged from the opening, and then the opening is heat sealed to form the upper seal. Then, the packaged semi-finished product is manufactured, and then the packaged semi-finished product is put into a retort kettle and subjected to retort treatment under conditions of retort treatment consisting of temperature, 120 ° C., pressure, 2.1 kgf / cm ² · G, time, 30 minutes. The curry-retort packaging product for preservation according to the present invention was manufactured.
The packaged product manufactured above was confirmed by seeing through the round hole-shaped non-printing region from the outer surface, and the heat-sealable coextrusion having a white layer from the portion conceived in the non-printing pattern region. The white layer portion of the laminated film was discolored to yellow, and it was confirmed that the retort treatment was performed accurately.

(1). First, the following resin compositions (a), (b), (c), and (d) were prepared.
(I). Resin composition constituting the first layer Functional polypropylene block copolymer (manufactured by Sun Aroma Co., Ltd., trade name, PC380A, density = 0.9 g / cm ³ , melt flow rate, MFR = 1.0 g / 10 min) 100 parts by weight, 0.5 parts by weight of synthetic silica, 0.05 parts by weight of erucic acid amide, and 0.05 parts by weight of ethylenebisoleic acid amide were sufficiently kneaded to prepare a resin composition.
(B). Resin composition constituting second layer Functional polypropylene block copolymer (trade name, PC380A, density = 0.9 g / cm ³ , melt flow rate, MFR = 1.0 g / 10 min, manufactured by Sun Aroma Co., Ltd.) 80.0 parts by weight and 20.0 parts by weight of titanium oxide as a white pigment were sufficiently kneaded to prepare a resin composition.
(C). Resin composition constituting third layer Functional polypropylene block copolymer (trade name, PC380A, density = 0.9 g / cm ³ , melt flow rate, MFR = 1.0 g / 10 min, manufactured by Sun Aroma Co., Ltd.) 73.5 parts by weight, Benzpyrene-free carbon black 1.5 parts by weight as a black pigment, and 25.0 parts by weight of titanium oxide as a white pigment were sufficiently kneaded to prepare an adhesive resin composition. did.
(D). Resin composition constituting the fourth layer Functional polypropylene block copolymer (trade name, PC380A, density = 0.9 g / cm ³ , melt flow rate, MFR = 1.0 g / 10 min, manufactured by Sun Aroma Co., Ltd.) 100 parts by weight, 0.5 parts by weight of synthetic silica, 0.05 parts by weight of erucic acid amide, and 0.05 parts by weight of ethylenebisoleic acid amide were sufficiently kneaded to prepare a resin composition.
Next, using each of the resin compositions prepared above, using a four-kind four-layer top-blown air-cooled inflation co-extrusion film-forming machine, the layer of the resin composition (a) is 10 μm, Co-extrusion of (b) a resin composition layer to 20 μm, (c) a resin composition layer to 10 μm, and (d) a resin composition layer to 30 μm, respectively, A heat-sealable coextruded laminated film having a white layer according to the present invention consisting of a coextruded inflation film having a total thickness of 70 μm was produced.
(2). On the other hand, a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm is used as the stretched resin film, which is mounted on the unwinding roll of the plasma chemical vapor deposition apparatus, and then conveyed at a line speed of 150 mm / min. Then, using a magnetron sputtering apparatus, introducing an argon gas of 600 sccm, performing plasma treatment at an output of 20 kW, forming a plasma-treated surface with an inert gas on the surface of the biaxially stretched polyethylene terephthalate film, Then, a 200 nm thick silicon oxide vapor deposition film was formed on the plasma treated surface under the following conditions.
(Deposition conditions)
Reaction gas mixing ratio: Hexamethyldisiloxane: Oxygen gas: Helium = 1.2: 5.0: 2.5 (Unit: Slm)
Ultimate pressure: 5.0 × 10 ^-5 mbar
Film forming pressure: 7.0 × 10 ⁻² mbar
Line speed: 150 m / min
Power: 35kW
Next, immediately after forming the silicon oxide vapor deposition film having a thickness of 200 mm as described above, a glow discharge plasma generator is used on the silicon oxide vapor deposition film surface, and the power is 9 kW, oxygen gas (O ₂ ): argon gas. (Ar) = 7.0: 2.5 (unit: Slm) is used, and oxygen / argon mixed gas plasma treatment is performed at a mixed gas pressure of 6 × 10 ⁻² mbar and a processing speed of 150 m / min. A plasma-treated surface having a surface tension of 54 dyne / cm or more improved on the surface of the silicon oxide vapor-deposited film was formed to produce a biaxially stretched polyethylene terephthalate film having a silicon oxide vapor-deposited film.
(3). Next, on the surface of the silicon oxide vapor-deposited film of the biaxially stretched polyethylene terephthalate film having the silicon oxide vapor-deposited film produced in the above (2), a portion of a non-printing region having a round hole shape having a diameter of 10 mm is removed. Then, a desired printed pattern is formed, and then a two-component curable urethane adhesive (main agent: polyester polyol, curing agent: aliphatic socyanate) is used on the printed pattern surface. -Applying 4.0 g / m ² (dry) to the thickness using a lacquer method to form an adhesive layer for laminating, and then having a thickness of 15 μm on the surface of the laminating adhesive layer. These biaxially stretched nylon 6 films were laminated with their corona-treated surfaces facing each other, and then both were laminated by dry lamination.
Next, the surface of the biaxially stretched nylon 6 film laminated as described above was subjected to corona discharge treatment, and then the corona treatment surface was subjected to a two-component curable urethane adhesive (main agent: polyester polyol) in the same manner as described above. -Glue, curing agent: aliphatic socyanate), and this is coated with a gravure roll coat method to a thickness of 4.0 g / m ² (dry) to form an adhesive layer for laminating. After forming, the heat-sealable coextruded laminated film having the white layer produced in (1) above is applied to the surface of the adhesive layer for laminating, and the layer of the resin composition of (i) The laminates according to the present invention were manufactured by laminating the two surfaces with each other and then laminating them by dry lamination.
(5). Next, two sheets of the laminated material produced above are prepared, and the heat-sealable coextruded laminated film having the white layer is overlapped with each other facing each other, and then an impulse sealer is used. A three-sided seal-type soft packaging bag having an opening at the top is formed by forming a seal part at the end of the periphery of the three-side heat seal, and a curry retort pouch. It was.
In the three-sided seal type soft packaging bag manufactured above, the curry is filled and packaged from the opening, and then the opening is heat sealed to form the upper seal. Then, the packaged semi-finished product is manufactured, and then the packaged semi-finished product is put into a retort kettle and subjected to retort treatment under conditions of retort treatment consisting of temperature, 120 ° C., pressure, 2.1 kgf / cm ² · G, time, 30 minutes. The curry-retort packaging product for preservation according to the present invention was manufactured.
The packaged product manufactured above was confirmed by seeing through the round hole-shaped non-printing region from the outer surface, and the heat-sealable coextrusion having a white layer from the portion conceived in the non-printing pattern region. The white layer portion of the laminated film was discolored to yellow, and it was confirmed that the retort treatment was performed accurately.

(1). First, the following resin compositions (a), (b), (c), (d), and (e) were prepared.
(I). Resin composition constituting the first layer Functional polypropylene block copolymer (manufactured by Sun Aroma Co., Ltd., trade name, PC380A, density = 0.9 g / cm ³ , melt flow rate, MFR = 1.0 g / 10 min) 100 parts by weight, 0.5 parts by weight of synthetic silica, 0.05 parts by weight of erucic acid amide, and 0.05 parts by weight of ethylenebisoleic acid amide were sufficiently kneaded to prepare a resin composition.
(B). Resin composition constituting second layer Functional polypropylene block copolymer (trade name, PC380A, density = 0.9 g / cm ³ , melt flow rate, MFR = 1.0 g / 10 min, manufactured by Sun Aroma Co., Ltd.) 80.0 parts by weight and 20.0 parts by weight of titanium oxide as a white pigment were sufficiently kneaded to prepare a resin composition.
(C). Resin composition constituting third layer Functional polypropylene block copolymer (trade name, PC380A, density = 0.9 g / cm ³ , melt flow rate, MFR = 1.0 g / 10 min, manufactured by Sun Aroma Co., Ltd.) 73.5 parts by weight, Benzpyrene-free carbon black 1.5 parts by weight as a black pigment, and 25.0 parts by weight of titanium oxide as a white pigment were sufficiently kneaded to prepare an adhesive resin composition. did.
(D). Resin composition constituting the fourth layer Functional polypropylene block copolymer (trade name, PC380A, density = 0.9 g / cm ³ , melt flow rate, MFR = 1.0 g / 10 min, manufactured by Sun Aroma Co., Ltd.) 80.0 parts by weight and 20.0 parts by weight of titanium oxide as a white pigment were sufficiently kneaded to prepare a resin composition.
(E). Resin composition constituting the fifth layer Functional polypropylene block copolymer (trade name, PC380A, density = 0.9 g / cm ³ , melt flow rate, MFR = 1.0 g / 10 min, manufactured by Sun Aroma Co., Ltd.) 100 parts by weight, 0.5 parts by weight of synthetic silica, 0.05 parts by weight of erucic acid amide, and 0.05 parts by weight of ethylene bisoleic acid amide were sufficiently kneaded to prepare a resin composition.
Next, using each of the resin compositions prepared above, using a five-type five-layer top-blown air-cooled inflation co-extrusion film forming machine, the layer of the resin composition of (a) is 10 μm, The layer of (b) resin composition is 20 μm, the layer of (c) resin composition is 10 μm, the layer of (d) resin composition is 10 μm, and the layer of (e) resin composition is 20 μm. A heat-sealable coextruded laminated film having a white layer according to the present invention consisting of 5 types and 5 layers of coextruded inflation film having a total thickness of 70 μm was produced by extrusion.
(2). Thereafter, in the same manner as in Example 2, a stretched resin film, a laminated material, a packaging bag, and a packaged product having an inorganic oxide vapor deposition film were produced in the same manner as in Example 2.

(1). First, the following resin compositions (a), (b), and (c) were prepared.
(I). Resin composition constituting first layer Ethylene-α / olefin copolymer (trade name, Evolu-SP2020, manufactured by Mitsui Chemicals, Ltd., density = 0.0.0) copolymerized using a single-site catalyst (metallocene catalyst). 916 g / cm ³ , melt flow rate, MFR = 1.5 g / 10 min) 100 parts by weight, 0.5 parts by weight of synthetic silica, 0.05 parts by weight of erucic acid amide, 0.05 parts by weight of ethylenebisoleic acid amide The resin composition was prepared by sufficiently kneading with parts by weight.
(B). Resin composition constituting the second layer Ethylene-α / olefin copolymer (trade name, Evolu-SP2020, density = 0.0.0, made by Mitsui Chemicals, Inc.) copolymerized using a single site catalyst (metallocene catalyst). A resin composition was prepared by sufficiently kneading 80.0 parts by weight of 916 g / cm ³ , melt flow rate, MFR = 1.5 g / 10 min) and 20.0 parts by weight of titanium oxide as a white pigment.
(C). Resin composition constituting the third layer Ethylene-α-olefin copolymer (trade name, Evolu-SP2020, density = 0.0.0, made by Mitsui Chemicals, Inc.) copolymerized using a single site catalyst (metallocene catalyst). 916 g / cm ³ , melt flow rate, MFR = 1.5 g / 10 min) 100 parts by weight, 0.5 parts by weight of synthetic silica, 0.05 parts by weight of erucic acid amide, 0.05 parts by weight of ethylenebisoleic acid amide The resin composition was prepared by sufficiently kneading with parts by weight.
Next, using each resin composition prepared above, using a three-type three-layer top-blown air-cooled inflation co-extrusion film forming machine, the layer of the resin composition of (A) is 10 μm, (B) A layer made of the resin composition of 20 μm and (c) a layer of the resin composition of 40 μm were coextruded to form a film of 3 types and 3 layers of coextruded inflation film with a total thickness of 70 μm. A heat sealable coextruded laminated film having a white layer according to the present invention was produced.
(2). On the other hand, a biaxially stretched nylon 6 film having a thickness of 15 μm was used as the stretched resin film, and this was mounted on a winding roll of a take-up vacuum deposition apparatus, and then the corona of the above biaxially stretched nylon 6 film. Without subjecting the treatment surface to plasma treatment with an inert gas, using aluminum as a vapor deposition source and supplying oxygen gas, a vacuum vapor deposition method using an electron beam (EB) heating method is performed under the following vapor deposition conditions. A vapor-deposited film of aluminum oxide having a thickness of 200 mm was formed.
(Deposition conditions)
Degree of vacuum in the deposition chamber; 2 × 10 ^-4 mbar
Degree of vacuum in winding chamber; 2 × 10 ^-2 mbar
Electron beam power: 25 kW
Film transport speed: 240 m / min
Next, immediately after forming the vapor deposition film of aluminum oxide having a thickness of 200 mm as described above, a glow discharge plasma generator is used on the vapor deposition film surface of the aluminum oxide, the power is 9 kW, oxygen gas (O ₂ ): argon gas (Ar) = 7.0: 2.5 (unit: Slm) is used, and oxygen / argon mixed gas plasma treatment is performed at a mixed gas pressure of 6 × 10 ⁻² mbar and a processing speed of 240 m / min. A biaxially stretched nylon 6 film having an aluminum oxide vapor deposition film was produced by forming a plasma treated surface in which the surface tension of the vapor deposition film surface of aluminum oxide was improved by 54 dyne / cm or more.
(3). Next, a desired printed pattern is formed on the corona-treated surface of a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm, except for a non-printed area having a round hole shape with a diameter of 10 mm. On the surface, a two-component curable urethane-based adhesive (main agent: polyester polyol, curing agent: aliphatic socyanate) is used, and the thickness is 4.0 g / m using a gravure roll coating method. ² (Dry) coating to form an adhesive layer for laminating, and then biaxial stretching having the deposited aluminum oxide film produced in (2) above on the surface of the laminating adhesive layer Nylon 6 film was laminated with its aluminum oxide vapor-deposited film facing each other, and then both layers were dry laminated.
Further, on the corona-treated surface of the biaxially oriented nylon 6 film of the biaxially oriented nylon 6 film having the vapor-deposited aluminum oxide film laminated as described above, a two-component curable urethane adhesive ( Main ingredient: Polyester polyol, Curing agent: Aliphatic socyanate), and apply this to a thickness of 4.0 g / m ² (dry) using a gravure roll coat method for laminating An adhesive layer is formed, and then a heat-sealable coextruded laminated film having the white layer produced in (1) above is applied to the surface of the adhesive layer for laminating, and the resin of (a) The layer surfaces of the composition were overlapped with each other facing each other, and then both were laminated by dry lamination to produce a laminate according to the present invention.
(4). Next, two sheets of the laminated material produced as described above are prepared, the heat-sealable coextruded laminated film faces are overlapped with each other, and then the outer periphery is formed using an impulse sealer. A three-sided seal-type soft packaging bag having an opening at the top while forming a seal part by three-sided heat-sealing at the peripheral ends was used as a boil sterilization pouch.
In the three-sided seal type soft packaging bag manufactured above, the boiled sardines are filled and packaged from the opening, and then the opening is heat sealed to form the upper seal. Then, the packaged semi-finished product is manufactured, and then the packaged semi-finished product is put into a boil pot and boiled under a boil treatment condition consisting of temperature, 100 ° C., time, 60 minutes, and boil sterilization for storage according to the present invention. A packaged product was manufactured.
The packaged product manufactured above was confirmed by seeing through the round hole-shaped non-printing region from the outer surface, and the heat-sealable coextrusion having a white layer from the portion conceived in the non-printing pattern region. The white layer portion of the laminated film was discolored to yellow, and it was confirmed that the boil treatment was performed accurately.

(1). First, the following resin compositions (a), (b), (c), and (d) were prepared.
(I). Resin composition constituting first layer Ethylene-α / olefin copolymer (trade name, Evolu-SP2020, manufactured by Mitsui Chemicals, Ltd., density = 0.0.0) copolymerized using a single-site catalyst (metallocene catalyst). 916 g / cm ³ , melt flow rate, MFR = 1.5 g / 10 min) 100 parts by weight, 0.5 parts by weight of synthetic silica, 0.05 parts by weight of erucic acid amide, 0.05 parts by weight of ethylenebisoleic acid amide The resin composition was prepared by sufficiently kneading with parts by weight.
(B). Resin composition constituting the second layer Ethylene-α / olefin copolymer (trade name, Evolu-SP2020, density = 0.0.0, made by Mitsui Chemicals, Inc.) copolymerized using a single site catalyst (metallocene catalyst). A resin composition was prepared by sufficiently kneading 80.0 parts by weight of 916 g / cm ³ , melt flow rate, MFR = 1.5 g / 10 min) and 20.0 parts by weight of titanium oxide as a white pigment.
(C). Resin composition constituting the third layer Ethylene-α-olefin copolymer (trade name, Evolu-SP2020, density = 0.0.0, made by Mitsui Chemicals, Inc.) copolymerized using a single site catalyst (metallocene catalyst). 916 g / cm ³ , melt flow rate, MFR = 1.5 g / 10 min) 73.5 parts by weight, Benzpyrene-free carbon black 1.5 parts by weight as a black pigment, and titanium oxide 25. 0 part by weight was sufficiently kneaded to prepare an adhesive resin composition.
(D). Resin composition constituting the fourth layer Ethylene-α-olefin copolymer (trade name, Evolu-SP2020, density = 0.0.0, made by Mitsui Chemicals, Inc.) copolymerized using a single site catalyst (metallocene catalyst). 916 g / cm ³ , melt flow rate, MFR = 1.5 g / 10 min) 100 parts by weight, 0.5 parts by weight of synthetic silica, 0.05 parts by weight of erucic acid amide, 0.05 parts by weight of ethylenebisoleic acid amide The resin composition was prepared by sufficiently kneading with parts by weight.
Next, using each of the resin compositions prepared above, using a four-kind four-layer top-blown air-cooled inflation co-extrusion film-forming machine, the layer of the resin composition (a) is 10 μm, Co-extrusion of (b) a resin composition layer to 20 μm, (c) a resin composition layer to 10 μm, and (d) a resin composition layer to 30 μm, respectively, A heat-sealable coextruded laminated film having a white layer according to the present invention consisting of a coextruded inflation film having a total thickness of 70 μm was produced.
(2). On the other hand, as a stretched resin film, a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm is used. First, the above-described biaxially stretched polyethylene terephthalate film is attached to a take-out roll of a take-up vacuum deposition apparatus, Next, this was fed out, and the corona-treated surface of the biaxially stretched polyethylene terephthalate film was subjected to vacuum deposition using an electron beam (EB) heating method while supplying oxygen gas using aluminum as a deposition source. According to the vapor deposition conditions, an aluminum oxide vapor deposition film having a thickness of 200 mm was formed.
(Deposition conditions)
Degree of vacuum in the deposition chamber; 2 × 10 ^-4 mbar
Degree of vacuum in winding chamber; 2 × 10 ^-2 mbar
Electron beam power: 25 kW
Film transport speed: 240 m / min Deposition surface: Corona-treated surface Next, immediately after forming the 200 nm thick aluminum oxide deposition film, a glow discharge plasma generator is used on the aluminum oxide deposition film surface. And a mixed gas pressure of 9 kw, oxygen gas (O ₂ ): argon gas (Ar) = 7.0: 2.5 (unit: Slm), and a mixed gas pressure of 6.0 × 10 ⁻² mbar, Oxygen / argon mixed gas plasma treatment is performed at a treatment speed of 240 m / min to form a plasma treatment surface in which the surface tension of the vapor deposition film surface of aluminum oxide is improved by 54 dyne / cm or more to have a vapor deposition film of aluminum oxide A biaxially stretched polyethylene terephthalate film was produced.
(3). Next, on the surface of the aluminum oxide vapor-deposited film of the biaxially stretched polyethylene terephthalate film having the aluminum oxide vapor-deposited film produced in the above (2), a portion of a non-printing area having a round hole shape with a diameter of 10 mm is excluded. Then, a desired printed pattern is formed, and then a two-component curable urethane adhesive (main agent: polyester polyol, curing agent: aliphatic socyanate) is used on the printed pattern surface. -Applying 4.0 g / m ² (dry) to the thickness using a lacquer method to form an adhesive layer for laminating, and then having a thickness of 15 μm on the surface of the laminating adhesive layer. These biaxially stretched nylon 6 films were laminated with their corona-treated surfaces facing each other, and then both were laminated by dry lamination.
Next, the surface of the biaxially stretched nylon 6 film laminated as described above was subjected to corona discharge treatment, and then the corona treatment surface was subjected to a two-component curable urethane adhesive (main agent: polyester polyol) in the same manner as described above. -Glue, curing agent: aliphatic socyanate), and this is coated with a gravure roll coat method to a thickness of 4.0 g / m ² (dry) to form an adhesive layer for laminating. After forming, the heat-sealable coextruded laminated film having the white layer produced in (1) above is applied to the surface of the adhesive layer for laminating, and the layer of the resin composition of (i) The laminates according to the present invention were manufactured by laminating the two surfaces with each other and then laminating them by dry lamination.
(5). Next, two sheets of the laminated material produced above are prepared, and the heat-sealable coextruded laminated film having the white layer is overlapped with each other facing each other, and then an impulse sealer is used. A three-sided seal-type soft packaging bag having an opening at the top and a three-sided heat-sealed end portion around the outer periphery of the pouch for boil sterilization is manufactured. It was.
In the three-sided seal type soft packaging bag manufactured above, the gob boiled and boiled are filled and packaged from the opening, and then the opening is heated and the upper seal is formed. Then, the packaged semi-finished product is manufactured, and then the packaged semi-finished product is put into a boil pot and boiled under a boil treatment condition consisting of temperature, 100 ° C., time, 60 minutes, and boil sterilization for storage according to the present invention. A packaged product was manufactured.
The packaged product manufactured above was confirmed by seeing through the round hole-shaped non-printing region from the outer surface, and the heat-sealable coextrusion having a white layer from the portion conceived in the non-printing pattern region. The white layer portion of the laminated film was discolored in yellow, and it was confirmed that the boil treatment was performed accurately.

(1). First, the following resin compositions (a), (b), (c), (d), and (e) were prepared.
(I). Resin composition constituting first layer Ethylene-α / olefin copolymer (trade name, Evolu-SP2020, manufactured by Mitsui Chemicals, Ltd., density = 0.0.0) copolymerized using a single-site catalyst (metallocene catalyst). 916 g / cm ³ , melt flow rate, MFR = 1.5 g / 10 min) 100 parts by weight, 0.5 parts by weight of synthetic silica, 0.05 parts by weight of erucic acid amide, 0.05 parts by weight of ethylenebisoleic acid amide The resin composition was prepared by sufficiently kneading with parts by weight.
(B). Resin composition constituting the second layer Ethylene-α / olefin copolymer (trade name, Evolu-SP2020, density = 0.0.0, made by Mitsui Chemicals, Inc.) copolymerized using a single site catalyst (metallocene catalyst). A resin composition was prepared by sufficiently kneading 80.0 parts by weight of 916 g / cm ³ , melt flow rate, MFR = 1.5 g / 10 min) and 20.0 parts by weight of titanium oxide as a white pigment.
(C). Resin composition constituting the third layer Ethylene-α-olefin copolymer (trade name, Evolu-SP2020, density = 0.0.0, made by Mitsui Chemicals, Inc.) copolymerized using a single site catalyst (metallocene catalyst). 916 g / cm ³ , melt flow rate, MFR = 1.5 g / 10 min) 73.5 parts by weight, Benzpyrene-free carbon black 1.5 parts by weight as a black pigment, and titanium oxide 25. 0 part by weight was sufficiently kneaded to prepare an adhesive resin composition.
(D). Resin composition constituting the fourth layer Ethylene-α-olefin copolymer (trade name, Evolu-SP2020, density = 0.0.0, made by Mitsui Chemicals, Inc.) copolymerized using a single site catalyst (metallocene catalyst). A resin composition was prepared by sufficiently kneading 80.0 parts by weight of 916 g / cm ³ , melt flow rate, MFR = 1.5 g / 10 min) and 20.0 parts by weight of titanium oxide as a white pigment.
(E). Resin composition constituting the fifth layer Ethylene-α / olefin copolymer (trade name, Evolu-SP2020, density = 0.0.0, made by Mitsui Chemicals, Inc.) copolymerized using a single site catalyst (metallocene catalyst). 916 g / cm ³ , melt flow rate, MFR = 1.5 g / 10 min) 100 parts by weight, 0.5 parts by weight of synthetic silica, 0.05 parts by weight of erucic acid amide, 0.05 parts by weight of ethylenebisoleic acid amide The resin composition was prepared by sufficiently kneading with parts by weight.
Next, using each of the resin compositions prepared above, using a three-type five-layer top-blown air-cooled inflation co-extrusion film forming machine, the layer of the resin composition of (A) is 10 μm, The layer of (b) resin composition is 20 μm, the layer of (c) resin composition is 10 μm, the layer of (d) resin composition is 10 μm, and the layer of (e) resin composition is 20 μm. A heat-sealable coextruded laminated film having a white layer according to the present invention consisting of three types and five layers of coextruded inflation film having a total thickness of 70 μm was produced by extrusion.
(2). Thereafter, in the same manner as in Example 5, a stretched resin film, a laminate, a packaging bag, and a packaged product having an inorganic oxide vapor deposition film were produced in the same manner as in Example 5.

  The present invention can accurately and easily confirm and judge the presence or absence of heat sterilization treatment such as boil treatment or retort treatment, and is excellent in filling and packaging suitability, content protection suitability, etc. A boil that is useful for filling and packaging mainly for boil and retort food and drink, fats and oils, frozen food and drink, preserved food and drink, etc. The present invention relates to a retort pouch.

It is a schematic sectional drawing which shows the layer structure of the example about the laminated material which comprises the pouch for boil retort which concerns on this invention. It is a schematic sectional drawing which shows the layer structure of the example about the laminated material which comprises the pouch for boil retort which concerns on this invention. It is a schematic sectional drawing which shows the layer structure of the example about the laminated material which comprises the pouch for boil retort which concerns on this invention. It is a schematic sectional drawing which shows the layer structure of the example about the laminated material which comprises the pouch for boil retort which concerns on this invention. It is a schematic perspective view which shows the structure of an example about the packaging bag concerning this invention manufactured by bag-making the laminated material which comprises the pouch for boil retort which concerns on this invention shown in said FIG. The boil / retort processing according to the present invention, in which the contents are packed in the packaging bag according to the present invention manufactured by bag-making the laminated material constituting the boil / retort pouch according to the present invention shown in FIG. It is a schematic perspective view which shows the structure of the example about packaged food. It is a schematic sectional drawing which shows the layer structure of the example about the heat-sealable coextrusion laminated film which has the white layer concerning this invention which forms the laminated material which comprises the pouch for boil retort which concerns on this invention. It is a schematic sectional drawing which shows the layer structure of the example about the heat-sealable coextrusion laminated film which has the white layer concerning this invention which forms the laminated material which comprises the pouch for boil retort which concerns on this invention. It is a schematic block diagram which shows an example of a low temperature plasma chemical vapor deposition apparatus. It is a schematic block diagram which shows an example of a winding-type vacuum deposition apparatus.

Explanation of symbols

A, A ₁ , A ₂ , A ₃ Laminated material B Packaging bag C Semi-wrapped product D Boiled / retort processed packaged food 1 Transparent part 1a Non-printing area 2 Stretched base film 3 White layer 4 Heat seal Extruded laminated film 5 Printing pattern 6 Inorganic vapor deposition film 7 Stretched resin film 11 Side seal part 12 Opening part 13 Contents 14 Upper seal part

Claims (7)

From a packaging bag formed by using a laminated material having a configuration in which at least a stretched base film having a fluoroscopic part and a heat-sealable coextruded laminated film having a white layer are laminated, A pouch for boil and retort. The stretched resin film having an inorganic oxide vapor deposition film is laminated between the stretched base film having a transparent portion and the heat-sealable coextruded laminated film having a white layer. The boil retort pouch according to claim 1. 3. The boil / retort pouch according to claim 1, wherein the see-through portion includes a non-printing area. The stretched substrate film is made of a biaxially stretched polyester resin film, a biaxially stretched polyamide resin film, or a biaxially stretched polyolefin resin film. A pouch for boil and retort as described in 1. 5. The pouch for boil / retort according to claim 1, wherein the stretched substrate film has an inorganic oxide vapor-deposited film on one surface thereof. A heat sealable coextrusion laminated film is a heat sealable coextrusion laminated film in which at least a transparent or translucent resin layer, a white resin layer, and a transparent or translucent resin layer are sequentially laminated. The pouch for boil / retort according to any one of claims 1 to 5, characterized by comprising: A heat-sealable co-extrusion laminated film is formed by sequentially laminating at least a transparent or translucent resin layer, a white resin layer, a light-shielding black or gray resin layer, and a transparent or translucent resin layer sequentially. 6. The boil / retort pouch according to any one of claims 1 to 5, wherein the pouch is a heat-sealable co-extruded laminated film.

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