JP5135738B2 - Seed wrapping material and seed bag - Google Patents

Description

  The present invention relates to a seed wrapping material whose contents can be observed from the outside, and a seed bag formed by molding the seed wrapping material.

  An increasing number of people enjoy planting gardens by putting planters on verandas or renting farms, and various vegetables and flower seeds stored in small bags are on the market. As such a seed wrapping material, paper or a bag-like material having a resin coating on its surface is often used, and it is common to print a picture or a photograph of seeds or florets on the surface.

Further, as a method of storing seeds, seeds were sealed in a container of the air-impermeable together with a deoxygenating agent, there is a method of storing at 30 ° C. below the temperature, oxygen permeability 50ml / m ² · atm · d following A method of storing seeds in a bag made of a packaging material is disclosed (Patent Document 1). The publication discloses a film in which vinylidene chloride or vinylidene chloride is laminated as the packaging material having the oxygen permeability.

In addition, it is necessary to disclose information such as seed type, planting time, management method, harvest time, etc. for seed wrapping materials. Usually, packaging materials made of paper base materials or paper base materials are coated with resin. In order to suppress oxygen ventilation, a packaging material in which an aluminum foil or the like is coated on a paper base material is often used.
JP 58-220611 A

  It is necessary to disclose a lot of information on the surface of the seed bag. Packaging materials made from paper base materials or paper base materials coated with resin can be printed easily on paper base materials. Information can be disclosed. However, since a paper base material is used, the contents cannot be observed from the outside of the packaging material. In addition, since the seed bags used in the kitchen garden are small bags, vegetables and florets at harvest time are generally printed, and the seeds are rarely printed, even if there are pictures, they are reduced and posted. There is a case. For this reason, it is convenient if the seeds can be observed directly without opening the bag, and if the contents can be confirmed directly, the enjoyment of the home garden increases and the consumer's willingness to purchase also improves.

  In addition, the seed bag needs to disclose information for each lot, such as the production location, germination rate, expiration date, and lot number. Therefore, it is convenient if such information can be easily written in a bag for each lot separately from printing general information such as seed name, soil type, sowing time, and sowing amount.

  Moreover, if excessive water vapor is present during storage of seeds, the seeds are steamed in the bag, fermentation and decay progress, and it becomes difficult to maintain the quality of the seeds. For this reason, the water vapor barrier property is also an important factor as a characteristic of the film-like seed packaging material used when producing the seed bag. Moreover, the strength which can protect the contents physically is necessary for using as a seed bag. However, when a metal foil such as an aluminum foil is used, the water vapor barrier property is excellent, but pinholes are easily generated, and as a result, the gas barrier property may be significantly impaired. Further, when incineration is performed as waste after use, the incineration suitability is inferior, and there is a problem that disposal after use is not easy. In addition, since vinylidene chloride and the like described in Patent Document 1 contain chlorine atoms in its structure, harmful chlorine gas is generated when incinerated as garbage after use, which is not preferable for environmental hygiene. Therefore, for seeds that have excellent gas barrier properties and safety after use, and that can protect the contents physically, have moderate flexibility, impact resistance, friction resistance, printability, openability, filling packaging suitability, etc. Wrapping materials and seed bags produced from such seed packaging materials are desired.

  In view of the above, an object of the present invention is to provide a seed wrapping material that is excellent in printability, has water vapor barrier properties, and allows the contents to be seen from the outside.

  Another object of the present invention is to provide a seed packaging material and a seed bag that can be easily disposed of after use.

  Furthermore, an object of the present invention is to provide a seed wrapping material and a seed bag having flexibility, impact resistance, friction resistance, printability, openability and filling / packaging suitability that can protect the contents. .

  As a result of examining the packaging material for seeds in detail, the present inventor constituted the packaging material for seeds with a laminated material having excellent gas barrier properties, and provided a printed layer between the layers constituting the laminated material, thereby providing a printed layer. The contents can be confirmed from the outside of the seed bag if it can be protected without being in contact with the outside, and the printed layer is printed by forming a window part with a white reflection density of 0.1 to 0.3. And, if the perforated portion of the window has the above-mentioned transparency, it has been found that the print can be easily read even when printed on the perforated portion different from the printed layer such as lot information. Completed.

That is, the first of the present invention is a seed packaging material in which at least a plastic base film, a printed layer, an inorganic oxide vapor deposition laminated film, and a heat seal layer are sequentially laminated from the outer surface side ,
The seed wrapping material has a window opening , and the printing layer on the outer peripheral portion other than the window opening is printed with white ink on the entire surface, and the white ink is positioned on the innermost surface of the printing layer. The printed layer of the window opening portion is made of white ink, and the window opening portion has a white reflection density of 0.1 to 0.3, and the inorganic oxide vapor-deposited laminated film is a base film layer. A seed packaging material, which is a laminated film provided with an inorganic oxide vapor deposition film on one surface thereof.

The second aspect of the present invention is a seed packaging material in which at least an inorganic oxide vapor-deposited laminated film, a printed layer, an intermediate base material, and a heat seal layer are sequentially laminated from the outer surface side ,
The seed wrapping material has a window opening , and the printing layer on the outer peripheral portion other than the window opening is printed with white ink on the entire surface, and the white ink is positioned on the innermost surface of the printing layer. The printed layer of the window opening portion is made of white ink, and the window opening portion has a white reflection density of 0.1 to 0.3, and the inorganic oxide vapor-deposited laminated film is a base film layer. A seed packaging material, which is a laminated film provided with an inorganic oxide vapor deposition film on one surface thereof.

  A third aspect of the present invention is a seed bag formed by molding the seed packaging material.

  The seed wrapping material of the present invention has a window opening portion with a white reflection density of 0.1 to 0.3 printed in a lighter color than the outer periphery, so the contents can be directly visually observed through the window opening portion. Can do. Moreover, since the white reflection density of the window opening is 0.1 to 0.3, the printed contents can be easily read even when the lot number is printed from the outside of the seed bag. Confirmation of contents and acquisition of lot information can be performed simultaneously by one window provided in the material.

  In addition, since the plastic packaging film or intermediate substrate is further laminated on the inorganic oxide vapor-deposited laminated film, the seed packaging material of the present invention is excellent in gas barrier properties and mechanical strength, chemical strength, and the like.

  Moreover, since the seed packaging material of the present invention is provided with a printed layer in any layer between the layers constituting the seed packaging material, the printed layer does not directly contact the outside, Excellent protection of clear printed surface.

  Hereinafter, the seed packaging material and seed bag of the present invention will be described in detail.

(1) Seed wrapping material The seed wrapping material used in the present invention has at least an inorganic oxide vapor-deposited laminated film and a heat seal layer laminated, and a plastic group on the base film layer side of the inorganic oxide vapor-deposited laminated film. A material film is laminated, or an intermediate base material is laminated between an inorganic oxide vapor-deposited laminated film and a heat seal layer. By having a plastic base film in the outermost layer, it is possible to ensure mechanical, physical, and chemical strength as a seed wrapping material, even if it does not have such a plastic base film, The said intensity | strength can be ensured by laminating | stacking an intermediate | middle base material between an inorganic oxide vapor deposition laminated | multilayer film and a heat seal layer.

  In the present invention, when the seed packaging includes a plastic base film, an inorganic oxide vapor-deposited laminated film, and a heat seal layer, the plastic base film / inorganic oxide vapor-deposited laminated film / heat seal layer is laminated, At this time, the plastic substrate film is preferably laminated so as to face the substrate film layer constituting the inorganic oxide vapor-deposited laminated film. Moreover, when including an inorganic oxide vapor deposition laminated | multilayer film, an intermediate | middle base material, and a heat seal layer, it is laminated | stacked in order of an inorganic oxide vapor deposition laminated | multilayer film / intermediate base material / heat seal layer. The laminated film is opposed to the inorganic oxide vapor-deposited film of the inorganic oxide vapor-deposited laminated film.

  In the present invention, in addition to the above constituent layers, other layers may be included. Such other layers include a surface treatment layer, for example, a laminating adhesive layer for laminating each layer by a dry laminating method, a primer layer when laminating a heat seal layer by a melt extrusion method, There are anchor coat layers and other undercoat agent layers.

  The seed packaging material used in the present invention has a printed layer on the plastic substrate film and / or the inorganic oxide vapor-deposited film, or a surface treatment layer thereof, and the seed packaging material has an intermediate substrate. In some cases, a printed layer is provided on the intermediate base material and / or the inorganic oxide vapor-deposited film, or a surface treatment layer thereof. Surface treatments suitable for clear printing include plasma treatment, corona discharge treatment, ozone treatment, low temperature plasma treatment, glow discharge treatment, etc., and a layer formed by application of primer, anchor coat, and laminating adhesive A printed layer can also be formed.

  Accordingly, the seed packaging material of the present invention including a plastic substrate film includes, for example, (a) <plastic substrate film / corona treatment layer / printing layer> / laminate adhesive layer / <corona treatment layer / substrate. Film layer / corona treatment layer / inorganic oxide deposition layer> / laminate adhesive layer / <corona treatment layer / heat seal layer>, (b) <plastic substrate film / corona treatment layer> / laminate adhesive layer / <Corona treatment layer / Base film layer / Corona treatment layer / Inorganic oxide deposition layer / Plasma treatment layer / Print layer> / Laminate adhesive layer / <Corona treatment layer / Heat seal layer>, (c) <Plastic group Material film / corona treatment layer> / adhesive layer for laminating / <corona treatment layer / base film layer / corona treatment layer / inorganic oxide deposition layer / plasma treatment layer / printing layer> / lamine Adhesive layer / <corona treatment layer / heat seal layer>, (d) <plastic substrate film / corona treatment layer> / laminate adhesive layer / <corona treatment layer / substrate film layer / corona treatment layer / Inorganic oxide vapor deposition layer / primer layer / printing layer> / laminate adhesive layer / <heat seal layer>, (e) <plastic base film / corona treatment layer> / laminate adhesive layer / <corona treatment layer / Examples include base film layer / corona treatment layer / inorganic oxide vapor deposition layer / primer layer / printing layer> / laminate adhesive layer / <corona treatment layer / heat seal layer>.

  Further, as the seed packaging material of the present invention including the intermediate base material, for example, (f) <base film layer / corona treatment layer / inorganic oxide vapor deposition layer / printing layer> / laminate adhesive layer / <corona Treatment layer / intermediate substrate> / adhesive layer for laminating / <corona treatment layer / heat seal layer>, (g) <substrate film layer / corona treatment layer / inorganic oxide deposition layer / primer layer / printing layer> / Laminate adhesive layer / <corona treatment layer / intermediate substrate> / laminate adhesive layer / <corona treatment layer / heat seal layer>, (h) <substrate film layer / corona treatment layer / inorganic oxide vapor deposition layer >> / laminate adhesive layer / <printing layer / corona treatment layer / intermediate substrate> / laminate adhesive layer / <corona treatment layer / heat seal layer>. Before forming the adhesive layer for laminating, a primer layer may be formed in advance, an anchor coating agent layer is provided in place of the laminating adhesive layer, and a heat seal layer is formed by a melt extrusion method. Also good.

  FIG. 1A is a seed packaging material in which a plastic base film, an inorganic oxide vapor-deposited laminated film, and a heat seal layer are laminated, and the base film of the plastic base film and the inorganic oxide vapor-deposited laminated film FIG. 1B is a cross-sectional view of a seed wrapping material having a printed layer between the layers. In FIG. 1B, an inorganic oxide vapor-deposited laminated film, an intermediate substrate, and a heat seal layer are laminated. The cross-sectional view of the packaging material for seeds which has a printing layer between a laminated film and an intermediate base material is shown.

  FIG. 1 (a) shows a plastic substrate film (10) provided with a printing layer (50) after providing a corona treatment layer (80), and a corona treatment layer (80) and an inorganic material on the substrate film layer (21). An inorganic oxide vapor-deposited laminated film (20) formed by sequentially laminating an oxide vapor-deposited layer (23) and a heat seal layer (30) having a corona-treated layer (80) are laminated via a laminate adhesive layer (70). It is a cross-sectional view of the seed packaging material bonded.

  Moreover, FIG.1 (b) is an inorganic oxide vapor deposition lamination | stacking which has a corona treatment layer (80), an aluminum vapor deposition layer (23), a primer layer (60), and a printing layer (50) in an inorganic oxide vapor deposition film (23). A film (20), an intermediate substrate (40) having a corona-treated layer (80) on both sides, and a heat seal layer (30) having a corona-treated layer (80) are interposed via a laminate adhesive layer (70). It is a cross-sectional view of the seed wrapping material formed by bonding.

  In the present invention, the printed layer (50) is printed such that a window portion (120) printed in a lighter color than the outer periphery is formed. FIG. 2 shows a seed bag prepared using the seed wrapping material (100). The window opening (120) is provided on either the front surface or the back surface of the seed bag, and this window opening ( 120) through which the contents can be observed.

(2) Plastic substrate film The plastic substrate that can be used in the present invention is excellent in mechanical, physical, and chemical strength sufficient for the use of the seed packaging material of the present invention. Resins that are excellent in pinhole property, puncture resistance, etc., can ensure a white reflection density in the window opening portion of 0.1 to 0.3, and can be printed on the surface can be widely used. . For example, at least one of a polyester resin, a polyamide resin, a polyaramid resin, a polypropylene resin, a polycarbonate resin, a polyacetal resin, a fluorine resin, and the like can be suitably used. In the present invention, a polypropylene resin can be particularly preferably used. It is preferable that the seed bag can be self-supporting when it is marketed, and if it is a polypropylene resin, it is excellent in mechanical and chemical strength and can give such a waist. Moreover, since the surface is glossy, the appearance of the seed bag can be improved. Further, printing by printing can be easily performed.

  In the present invention, the plastic substrate film may be any of an unstretched film of the resin and a film stretched in a uniaxial direction or a biaxial direction. In the present invention, it is particularly preferable to use a stretched nylon film, a biaxially stretched polyethylene terephthalate film or a biaxially stretched polypropylene film.

  In the present invention, the thickness of the plastic substrate film is not particularly limited as long as strength, puncture resistance, rigidity and the like can be ensured, but is preferably 6 to 100 μm, more preferably 9 to 50 μm.

(3) Printed layer In this invention, a printed layer is provided in a plastic base film or an inorganic oxide vapor deposition film, or these surface treatment layers. The printing method is not limited, but gravure printing is preferred. Gravure printing is a type of printing method in which the ink-applied portion of the original plate is engraved in a concave shape. In recent years, this concave portion is digitally formed by an etching machine equipped with a diamond laser. Since the ink comes out of the recess, the color density can be adjusted by the depth and size of the ink, the pressure of the recess on the printing layer, and the like. The gravure printing machine has one printing unit for each color and is excellent in reproducibility of images having gradation such as photographs. In order to print on a plastic film with such a gravure printing machine, it is common to perform backside printing on the side opposite to the side on which characters are viewed in order to prevent the printed layer from peeling off. In this order, for example, in order of black, indigo, red, and yellow, printing starts with light ink such as white ink. The entire surface printing with a light color ink such as white ink prevents the contents from being seen through, and the color printing layer provided between the light color ink such as the white ink and the plastic film can be made clear. It is. In the present invention, the printing layer is preferably white ink printing among the light inks as the uppermost layer of the printing layer, similarly to the above-described back surface printing. In the case of light ink, even when individual printing such as a lot number is performed on the window opening portion from the outside, the printed content can be easily read. Moreover, it excels in the effect which cuts out all the light rays containing an ultraviolet-ray, and is excellent also in the preservability of a seed. At this time, the order of the other color inks is not limited, but it is preferable to print in the order of black , indigo, red, and yellow, and print with the special color ink blended at a specific ratio after yellow. In the present invention, means having high brightness and light color inks, it means a white ink.

  FIG. 3 illustrates a method of forming a window opening portion printed on the printed layer in a lighter color than the outer periphery in the printing order in the corona treatment layer (80) of the plastic substrate film (10). First, in FIG. 3, black (51), indigo (52), red (53), yellow (54) and specific ink (55) are printed on the outer peripheral portion (57) other than the window opening portion (58), The window opening (58) is formed with a window opening (58) that is not printed with black, indigo, red, yellow and special color inks. Next, printing with white ink (56) is performed on both the window opening portion (58) and the outer peripheral portion (57). As a result, a printed layer of white ink (56) is also formed in the window opening (58). In FIG. 3, each color ink is illustrated in layers, but in each layer, the ink exists in dots, and a specific character or picture is represented by a set of dots of each color.

  In the present invention, the white reflection density of the window opening (58) is 0.1 to 0.3, more preferably 0.15 to 0.25. If it is less than 0.1, in the seed bag manufactured using the seed wrapping material, it may be difficult to read the printed surface even if printing is performed on the upper surface of the window opening portion from the outside. On the other hand, if it exceeds 0.3, the contents stored in the seed bag may be difficult to observe. In addition, the said transmittance | permeability in this invention shall be measured by the method described in the Example mentioned later.

  In the present invention, in order to adjust the transmittance, the size of the concave portion by the white ink of the gravure printing machine is adjusted, the number of concave portions per unit area of the printing layer is adjusted, or the window opening portion ( 58) may be formed with a plurality of fine lines of white ink, and the pattern may be formed within a range not impairing the gist of the present invention.

  In the present invention, there is no limitation on the size of the window opening part, the size of the seed bag manufactured using the seed packaging material of the present invention, the type of seed to be stored, the internal capacity printed on the upper surface of the window opening part, etc. Can be appropriately selected.

  The printing layer is composed of one or more ordinary ink vehicles as the main component, and if necessary, a plasticizer, a stabilizer, an antioxidant, a light stabilizer, an ultraviolet absorber, a curing agent, and a crosslinking agent. Add one or more additives such as additives, lubricants, antistatic agents, fillers, etc., add colorants such as dyes and pigments, and use solvents, diluents, etc. An ink composition obtained by kneading to prepare an ink composition can be used. As such an ink vehicle, known ones such as sesame oil, drill oil, soybean oil, hydrocarbon oil, rosin, rosin ester, rosin modified resin, shellac, alkyd resin, phenolic resin, maleic resin, Natural resin, hydrocarbon resin, polyvinyl chloride resin, polyacetic acid resin, polystyrene resin, polyvinyl butyral resin, acrylic or methacrylic resin, polyamide resin, polyester resin, polyurethane resin, epoxy resin, urea resin , Melamine resin, amino alkyd resin, nitrocellulose, ethyl cellulose, chlorinated rubber, cyclized rubber, etc. can be used alone or in combination.

  Although the above was demonstrated by gravure printing, printing systems, such as letterpress printing, screen printing, transfer printing, flexographic printing, etc., may be sufficient.

(4) Base film layer The base film layer constituting the inorganic oxide vapor-deposited laminated film has mechanical, physical, and chemical strengths sufficient to provide an inorganic oxide vapor-deposited film. It is preferable to use a resin film that can withstand the conditions for forming the film and can satisfactorily maintain without deteriorating the properties of the inorganic oxide vapor-deposited film.

  Examples of such a base film layer include polyethylene resin, polypropylene resin, cyclic polyolefin resin, fluorine resin, polystyrene resin, acrylonitrile-styrene copolymer (AS resin), and acrylonitrile-butadiene-styrene copolymer. (ABS resin), polyvinyl chloride resin, fluorine resin, poly (meth) acrylic resin, polycarbonate resin, polyester resins such as polyethylene terephthalate and polyethylene naphthalate, polyamide resins such as various nylons, polyimide resins Resin, Polyamideimide resin, Polyarylphthalate resin, Silicone resin, Polysulfone resin, Polyphenylene sulfide resin, Polyethersulfone resin, Polyurethane resin, Acetal resin, Cellulose Fat, can be used films composed of various resins other like. In particular, a film of a polypropylene resin, a polyester resin, or a polyamide resin is preferable.

  One or more of the above resins are used, and the resin is formed into a single layer using a film forming method such as an extrusion method, a cast molding method, a T-die method, a cutting method, an inflation method, or the like. Or two or more types of resin formed into a multilayer film by co-extrusion or the like, or a mixture of two or more types of resin to form a film, and a tenter method or a tubular method, etc. Various resin films formed by stretching in the axial direction can be used.

  In this invention, as a film thickness of a base film, about 6-100 micrometers, More preferably, about 9-50 micrometers is preferable.

  It should be noted that one or more of the above resins are used, and in forming the film, for example, film processability, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, slipperiness, mold release, etc. Various plastic compounding agents and additives can be added for the purpose of improving and modifying properties, flame retardancy, anti-fungal properties, electrical properties, strength, etc. From a very small amount to several tens of percent, it can be arbitrarily added depending on the purpose.

  In the above, general additives include, for example, colorants such as lubricants, crosslinking agents, antioxidants, ultraviolet absorbers, light stabilizers, fillers, antistatic agents, lubricants, antiblocking agents, dyes, pigments and the like. Others can be arbitrarily used, and further, a modifying resin or the like can also be used.

(5) Surface treatment In this invention, when forming an inorganic oxide vapor deposition film in a base film layer, it is preferable to surface-treat beforehand. Moreover, when forming a printing layer in a plastic base film, an intermediate base material, and an inorganic oxide vapor deposition film, it is preferable to surface-treat these. Thereby, the adhesiveness between each layer can be improved. In addition, when laminating and bonding, if the surface treatment is performed in advance, the adhesion between the layers can be improved. In the present invention, any other layer may be surface treated.

Such surface treatments include corona discharge treatment, ozone treatment, low temperature plasma treatment using oxygen gas or nitrogen gas, glow discharge treatment, oxidation treatment using chemicals, etc., and other pretreatments, etc. is there. Corona discharge treatment increases the strength of adhesion and thermal welding by causing corona discharge on the surface of the object to cause phenomena such as physical unevenness of the treated surface and oxidation of the chemical structure near the surface. It is done for the purpose. The processing conditions of the corona discharge treatment are a discharge gap of 1 to 15 mm, a substrate feed speed of 100 to 1000 cm / min, and a treatment strength of 300 to 1000 W / m ² / min.

  Further, a primer, an undercoat, an anchor coat or the like may be optionally applied in advance to the surface of various films used in the present invention for surface treatment.

(6) Inorganic oxide vapor-deposited film As the inorganic oxide vapor-deposited film, for example, a chemical vapor deposition method, a physical vapor deposition method or a combination thereof, It can be produced by forming a multilayer film or a composite film comprising two or more layers.

  Examples of the chemical vapor deposition method include chemical vapor deposition methods such as plasma chemical vapor deposition method, low temperature plasma chemical vapor deposition method, thermal chemical vapor deposition method, and photochemical vapor deposition method (Chemical Vapor Deposition method), CVD method). Specifically, on one surface of the base film layer, a monomer gas for vapor deposition such as an organosilicon compound is used as a raw material, an inert gas such as argon gas or helium gas is used as a carrier gas, and oxygen is supplied. An inorganic oxide vapor deposition film such as silicon oxide can be formed by using a low temperature plasma chemical vapor deposition method using an oxygen gas or the like as a gas and using a low temperature plasma generator or the like.

  In the above, as a low temperature plasma generator, generators, such as high frequency plasma, pulse wave plasma, and microwave plasma, can be used, for example. In view of obtaining highly active and stable plasma, it is preferable to use a high-frequency plasma generator.

  An example of a method for forming an inorganic oxide vapor deposition film by the low temperature plasma chemical vapor deposition method will be described with reference to FIG. 4 which is a schematic configuration diagram of a low temperature plasma chemical vapor deposition apparatus.

  In the present invention, the base film layer 201 is unwound from the unwinding roll 223 disposed in the vacuum chamber 222 of the plasma chemical vapor deposition apparatus 221, and the base film layer 201 is further passed through the auxiliary roll 224 in a predetermined manner. At the speed of cooling / conveying on the circumferential surface of the electrode drum 225. On the other hand, a gas mixture for vapor deposition is prepared by supplying vapor deposition monomer gas such as oxygen gas, inert gas, organosilicon compound, etc. from the gas supply devices 226, 227 and the raw material volatilization supply device 228, etc. Is introduced into the vacuum chamber 222 through the raw material supply nozzle 229. The vapor deposition mixed gas composition is supplied onto the substrate film layer 201 transported on the cooling / electrode drum 225 circumferential surface, and plasma is generated and irradiated by glow discharge plasma 230 to irradiate inorganic oxide such as silicon oxide. A product vapor deposition film is formed. Next, if the base film layer 201 on which the inorganic oxide vapor deposition film such as silicon oxide is formed is wound around the winding roll 234 via the auxiliary roll 233, the inorganic oxide vapor deposition film formed by the plasma chemical vapor deposition method is formed. Can be formed. A predetermined power is applied to the cooling / electrode drum 225 from a power source 231 disposed outside the vacuum chamber 222, and a magnet 232 is disposed in the vicinity of the cooling / electrode drum 225 to promote plasma generation. Has been. Since a predetermined voltage is applied from the power source to the cooling / electrode drum in this way, 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. When the substrate film layer is conveyed at a constant speed in this state, the glow discharge plasma causes the cooling / electrode drum peripheral surface to be cooled. An inorganic oxide vapor deposition film such as silicon oxide can be formed on the upper base film layer. In FIG. 4, reference numeral 235 represents a vacuum pump.

In the present invention, 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 preferable to do.

The raw material volatilization supply device volatilizes the organic silicon compound as the raw material, mixes it with oxygen gas, inert gas, etc. supplied from the gas supply device, and introduces this mixed gas into the vacuum chamber through the raw material supply nozzle. . At this time, the content of the organosilicon compound in the mixed gas is preferably 1 to 40%, the oxygen gas content is 10 to 70%, and the inert gas content is preferably 10 to 60%. For example, the mixing ratio of organosilicon compound: oxygen gas: inert gas can be about 1: 6: 5 to 1:17:14. Note that the degree of vacuum in the vacuum chamber when supplying the organosilicon compound, the inert gas, the oxygen gas, and the like is 1 × 10 ⁻¹ to 1 × 10 ⁻⁴ Torr, preferably 1 × 10 ⁻¹ to 1 × 10 ⁻² Torr is preferable, and the conveying speed of the base film layer is 10 to 300 m / min, preferably 50 to 150 m / min. Formation of an inorganic oxide vapor deposition film such as silicon oxide obtained in this way is formed on the base film layer in the form of a thin film in the form of SiO _x while oxidizing the plasma-formed source gas with oxygen gas. Therefore, the formed inorganic oxide vapor deposition film such as silicon oxide is a dense continuous layer having a small gap and a high flexibility. Therefore, the barrier property of the inorganic oxide vapor deposition film such as silicon oxide is the conventional one. It is much higher than an inorganic oxide vapor deposition film such as silicon oxide formed by vacuum vapor deposition or the like, and a sufficient barrier property can be obtained with a thin film thickness. Moreover, since the surface of the base film layer is cleaned by the SiO _x plasma and polar groups, free radicals, etc. are generated on the surface of the base film layer, the inorganic oxide vapor deposition film such as silicon oxide formed on the base The tight adhesion with the material film layer is high. Further, the degree of vacuum when forming a continuous film of an inorganic oxide such as silicon oxide is 1 × 10 ⁻¹ to 1 × 10 ⁻⁴ Torr, preferably 1 × 10 ⁻¹ to 1 × 10 ⁻² Torr. In addition, since the degree of vacuum when forming an inorganic oxide deposited film such as silicon oxide by a conventional vacuum deposition method is lower than 1 × 10 ⁻⁴ to 1 × 10 ⁻⁵ Torr, It is possible to shorten the vacuum state setting time when the film layer is exchanged, and the degree of vacuum is easily stabilized, and the film forming process is also stabilized.

In the present invention, a vapor deposition film of silicon oxide formed using a vapor deposition monomer gas such as an organosilicon compound chemically reacts with a vapor deposition monomer gas such as an organosilicon compound and oxygen gas, and the reaction product is It closely adheres to one surface of the base film layer to form a dense, flexible thin film, and is usually represented by the general formula SiO _x (where X represents a number from 0 to 2). It is a continuous thin film mainly composed of silicon oxide. The silicon oxide vapor deposition film is a silicon oxide vapor deposition represented by the general formula SiO _x (where X represents a number from 1.3 to 1.9) in terms of transparency and barrier properties. A thin film mainly composed of a film is preferable. The value of X varies depending on the molar ratio of vapor deposition monomer gas and oxygen gas, plasma energy, etc. Generally, the gas permeability decreases as the value of X decreases, but the film itself is yellow. The transparency becomes worse.

In the present invention, the silicon oxide vapor-deposited film is mainly composed of silicon oxide, and further contains at least one compound of carbon, hydrogen, silicon or oxygen, or a compound composed of two or more elements by chemical bonding or the like. It consists of a vapor deposition film. 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, or the like, the raw material organosilicon compound or a derivative thereof is further added. It may be contained by a chemical bond or the like. Examples thereof include hydrocarbons having a CH ₃ site, hydrosilica such as SiH ₃ silyl and 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 silicon oxide vapor deposition film can be varied by changing the conditions of the vapor deposition process. At this time, the content of the above-mentioned compound in the deposited film of silicon oxide is 0.1 to 50%, preferably 5 to 20%. When 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, and high barrier properties are achieved. On the other hand, it may be difficult to maintain stably, and if it exceeds 50%, the barrier property may be lowered.

  Further, in the present invention, in the silicon oxide vapor-deposited film, it is preferable that the content of the above compound decreases in the depth direction from the surface of the silicon oxide vapor-deposited film. As a result, the impact resistance and the like are enhanced by the above-mentioned compound and the like on the surface of the silicon oxide vapor-deposited film. On the other hand, since the content of the above-mentioned compound is small at the interface with the base film layer, The tight adhesion with the deposited film becomes strong.

  In the present invention, the above-described vapor deposition film of silicon oxide uses, for example, a surface analyzer such as an X-ray photoelectron spectrometer (Xray), a secondary ion mass spectrometer (Secondary Ion Mass Spectroscopy, SIMS), or the like. The above-mentioned physical properties can be confirmed by performing analysis such as ion etching in the vertical direction and performing elemental analysis of the deposited film of silicon oxide.

  In the present invention, the thickness of the silicon oxide vapor-deposited film is preferably about 50 to 4000 mm, more preferably 100 to 1000 mm. If it is thicker than 4000 mm, cracks or the like may occur in the film. On the other hand, if it is less than 50 mm, it may be difficult to achieve a barrier effect. 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. As a means for changing the film thickness of the silicon oxide vapor deposition film, a method of increasing the volume velocity of the vapor deposition film, that is, a method of increasing the amount of monomer gas and oxygen gas, a method of slowing the vapor deposition rate, etc. be able to.

  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 the material to be used is one type or two or more types. It is also possible to form an inorganic oxide vapor-deposited film mixed with different materials.

  In the present invention, as a monomer gas for vapor deposition of an organic silicon compound or the like that forms an inorganic oxide vapor deposition film such as silicon oxide, for example, 1,1,3,3-tetramethyldisiloxane, hexamethyldisiloxane, vinyltrimethyl Silane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, Methyltriethoxysilane, octamethylcyclotetrasiloxane, etc. can be used. Among these, it is particularly preferable to use 1,1,3,3-tetramethyldisiloxane or hexamethyldisiloxane as a raw material because of its handleability and the characteristics of the formed continuous film. In the above, as the inert gas, for example, argon gas, helium gas, or the like can be used.

  On the other hand, in the present invention, an inorganic oxide vapor deposition film can also be formed by physical vapor deposition. As such a physical vapor deposition method, for example, an inorganic oxide deposition is performed by a physical vapor deposition method (Physical Vapor Deposition method, PVD method) such as a vacuum deposition method, a sputtering method, an ion plating method, an ion cluster beam method, or the like. A film can be formed.

  Specifically, using a metal oxide as a raw material, heating and evaporating it, and vacuum-depositing this on one of the base film layers, or using a metal oxide as a raw material, Forming a deposited film using an oxidation reaction deposition method in which oxygen is introduced and oxidized to deposit on one of the base film layers, and further a plasma-assisted oxidation reaction deposition method in which the oxidation reaction is supported by plasma. Can do. In addition, as a heating method of 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. A method of forming a thin film of an inorganic oxide by physical vapor deposition will be described with reference to FIG. 5 showing a schematic configuration diagram showing an example of a take-up vacuum deposition apparatus.

  First, the base film layer 201 fed out from the unwinding roll 243 is guided to the cooled coating drum 246 via the guide rolls 244 and 245 in the vacuum chamber 242 of the wind-up type vacuum deposition apparatus 241. The deposition source 248 heated by the crucible 247, for example, metal aluminum or aluminum oxide is evaporated on the base film layer 201 guided on the cooled coating drum 246, and if necessary. Then, an oxygen gas or the like is ejected from the oxygen gas outlet 249 and an inorganic oxide vapor deposition film such as aluminum oxide is formed through the masks 250 and 250 while supplying the oxygen gas. The base film layer 201 on which an inorganic oxide vapor deposition film such as aluminum oxide is formed is sent out through the guide rolls 251 and 252 and wound up on the take-up roll 253, whereby an inorganic oxide vapor deposition film formed by physical vapor deposition is formed. Can be formed. In addition, the inorganic oxide vapor deposition film of the 1st layer is formed first using the said winding-type vacuum evaporation apparatus, Then, an inorganic oxide vapor deposition film is further formed on it, or the said winding-type vacuum evaporation The apparatus may be connected in series, and an inorganic oxide vapor deposition film may be continuously formed to form an inorganic oxide vapor deposition film composed of a multilayer film of two or more layers.

The inorganic oxide vapor deposition film may basically be a thin film on which a metal oxide is vapor-deposited. For example, silicon (Si), aluminum (Al), magnesium (Mg), calcium (Ca), potassium ( Use vapor-deposited films of metal oxides such as K), tin (Sn), sodium (Na), boron (B), titanium (Ti), lead (Pb), zirconium (Zr), yttrium (Y) Can do. Preferably, a vapor-deposited film of a metal oxide such as silicon (Si) or aluminum (Al) can be used. Therefore, the metal oxide vapor deposition film can be referred to as a metal oxide such as silicon oxide, aluminum oxide, magnesium oxide, and the like, 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.

  In addition, as the range of the value of X, silicon (Si) exceeds 0 and 2 or less, aluminum (Al) exceeds 0 and 1.5 or less, magnesium (Mg) exceeds 0 and 1 or less, calcium (Ca ) Is greater than 0 and less than or equal to 1, potassium (K) is greater than 0 and less than or equal to 0.5, tin (Sn) is greater than 0 and less than or equal to 2, sodium (Na) is greater than 0 and less than or equal to 0.5, and boron (B) is 0 to 1, 5 or less, Titanium (Ti) is more than 0 to 2 or less, Lead (Pb) is more than 0 to 1 or less, Zirconium (Zr) is more than 0 to 2 or less, Yttrium (Y) is more than 0 to 1 .5 or less. In the above, when X = 0, it is a complete metal, and the upper limit of the range of X is a completely oxidized value. The present invention is characterized by having a window opening portion with a white reflection density of 0.1 to 0.3. Generally, examples other than silicon (Si) and aluminum (Al) are poor. . Therefore, in the present invention, silicon or aluminum is preferable as M. In this case, the value of X is 1.0 to 2.0 for silicon (Si) and 0.5 to 1.5 for aluminum (Al). It is a range. In addition, although the film thickness of an inorganic oxide vapor deposition film changes with kinds etc. of the metal to be used or a metal oxide, it can be arbitrarily selected within the range of, for example, 50 to 2000 mm, preferably 100 to 1000 mm. . Moreover, as an inorganic oxide vapor deposition film, the metal or metal oxide to be used can be used by 1 type, or 2 or more types of mixture, and can comprise the inorganic oxide vapor deposition film mixed with the dissimilar material. .

  Furthermore, in the present invention, for example, a composite film composed of two or more layers of different kinds of vapor-deposited inorganic oxide films can be formed by using both physical vapor deposition and chemical vapor deposition.

  As a composite film consisting of two or more layers of the above-mentioned different types of inorganic oxide vapor-deposited films, first, on the base film layer, a chemical vapor deposition method is used. An inorganic oxide vapor deposition film capable of preventing the above is provided, and then an inorganic oxide vapor deposition film formed by physical vapor deposition is provided on the inorganic oxide vapor deposition film to form an inorganic oxide composed of a composite film composed of two or more layers. It is preferable to constitute a material vapor deposition film. Contrary to the above, an inorganic oxide vapor deposition film is first provided on the base film layer by physical vapor deposition, and then dense and flexible by chemical vapor deposition. It is also possible to provide an inorganic oxide vapor deposition film composed of a composite film composed of two or more layers by providing an inorganic oxide vapor deposition film that can relatively prevent the occurrence of cracks.

(7) Primer layer In the present invention, for example, a primer is applied to the surface of the inorganic oxide vapor-deposited film to form a primer layer, and then an adhesive layer for laminating is formed on the surface of the primer layer. A substrate such as a heat seal layer can be laminated using a dry laminate lamination method through the layer and the laminating adhesive layer. By providing such a primer layer, the adhesion strength between the inorganic oxide vapor-deposited film and the adhesive layer for laminating, the anchor coat layer, the heat seal layer, etc., which can be laminated thereon, is improved, and the lamination strength is improved. Can do. Moreover, a primer layer may be formed on the surface of the inorganic oxide vapor-deposited film, and a printed layer may be formed thereon.

As a primer constituting the primer layer, a polyurethane resin, a polyester resin or the like is a main component of the vehicle, and a silane coupling agent 0.05 to 10% with respect to 1 to 30% by mass of the polyurethane resin or polyester resin. A primer composition containing a mass and preferably 0.1 to 5 mass%, a filler of 0.1 to 20 mass%, preferably 1 to 10 mass%, and additionally containing a solvent and a diluent is used. be able to. If necessary, the primer composition may further contain a stabilizer, a curing agent, a crosslinking agent, a lubricant, an ultraviolet absorber, and other additives. In the present invention, the primer layer has a thickness of 0.1 to 10.0 g / m ² (dry state). The primer composition is coated by roll coating, gravure coating, knife coating, dip coating, spray coating, other coating methods, etc., the coating film is dried to remove the solvent and diluent, and if necessary An aging process etc. can be performed and it can be set as a primer layer.

  As the polyurethane resin, a polyurethane resin obtained by a reaction between a polyfunctional isocyanate and a hydroxyl group-containing compound can be used. For example, polyfunctional isocyanates such as aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate, or aliphatic polyisocyanates such as hexamethylene diisocyanate, xylylene diisocyanate. And a one-component or two-component curable polyurethane resin obtained by a reaction between a polyether-based polyol, a polyester-based polyol, a polyacrylate polyol, and other hydroxyl group-containing compounds.

  On the other hand, as a polyester resin, thermoplasticity produced by polycondensation of one or more aromatic saturated dicarboxylic acids having a benzene nucleus as a basic skeleton such as terephthalic acid and one or more saturated dihydric alcohols. Can be exemplified. Examples of the aromatic saturated dicarboxylic acid having a benzene nucleus include terephthalic acid, isophthalic acid, phthalic acid, diphenyl ether, and 4,4-dicarboxylic acid. Moreover, as saturated dihydric alcohol, ethylene glycol, propylene glycol, trimethylene glycol, tetramethylene glycol, diethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, hexamethylene glycol, dodecamethylene glycol, neopentyl glycol, etc. Examples thereof include alicyclic glycols such as fatty acid glycol and cyclohexasandimethanol, 2,2-bis (4′-β-hydroxyethoxyphenyl) propane, naphthalenediol and other aromatic diols.

  More specifically, as the polyester-based resin, a thermoplastic polyethylene terephthalate resin produced by polycondensation of terephthalic acid and ethylene glycol, and a thermoplastic polybutylene terephthalate resin produced by polycondensation of terephthalic acid and tetramethylene glycol. , Thermoplastic polycyclohexanedimethylene terephthalate resin produced by polycondensation of terephthalic acid and 1,4-cyclohexanedimethanol, thermoplastic polyethylene terephthalate resin produced by copolycondensation of terephthalic acid, isophthalic acid and ethylene glycol, terephthalate Thermoplastic polyethylene terephthalate resin produced by copolycondensation of acid, ethylene glycol and 1,4-cyclohexanedimethanol, terephthalic acid, isophthalic acid and ethylene glycol Thermoplastic polyethylene terephthalate resin produced by copolycondensation of propylene glycol, polyester polyol resins, and other like.

  In addition to saturated aromatic dicarboxylic acid having a benzene nucleus, one or more aliphatic saturated dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanoic acid And may be copolycondensed, and the amount used is preferably in the range of 1 to 10% by mass of the aromatic dicarboxylic acid.

  According to the polyurethane resin or polyester resin, the adhesion between the inorganic oxide, particularly the organic-containing silicon oxide layer, the printed layer, the heat seal layer, etc. can be improved, and the degree of elongation of the primer layer can be improved. Thus, suitability for post-processing such as laminating can be improved, and the occurrence of cracks in the organic-containing silicon oxide layer during post-processing can be prevented.

  As the silane coupling agent constituting the primer composition, organic functional group silane monomers having binary reactivity can be used. For example, γ-chloropropyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane , Vinyl-tris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethylmethoxysilane, γ-glycidoxypropyltrimethoxysilane, vinyltriacetoxysilane , Γ-mercaptopropylmethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-ureidopropyltriethoxysilane, bis ( β-hydroxye Le)-.gamma.-aminopropyltriethoxysilane, .gamma.-aminopropyl one such as an aqueous solution of silicones alone or may be used in combination of two or more.

  In the present invention, the inorganic functional group and / or organic functional group of the silane coupling agent can be used to increase the adhesive strength between the inorganic oxide vapor-deposited film and the printed layer, primer layer, or the like. Specifically, a functional group at one end of the molecule of the silane coupling agent, usually a chloro, alkoxy, or acetoxy group, is hydrolyzed to form a silanol group (SiOH), which forms an inorganic oxide deposited film. It reacts with the constituent metal and active groups on the film surface, for example, a functional group such as a hydroxyl group, causing a reaction such as a dehydration condensation reaction, and a silane coupling agent is covalently bonded to the film surface of the inorganic oxide deposited film. Further, a strong bond is formed by adsorption or hydrogen bonding on the surface of the inorganic oxide vapor deposition film of the silanol group itself. Also, an organic functional group such as vinyl, methacryloxy, amino, epoxy, or mercapto at the other end of the silane coupling agent is formed on the thin film of the silane coupling agent, for example, for printing layers, primer layers, and laminates. It reacts with the substances constituting the adhesive layer, anchor coat layer, melt-extruded resin layer, and other layers to form a strong bond. Further, the above-mentioned printing layer, primer layer, adhesive layer for lamination, anchor coat layer, Through the melt-extruded resin layer, the heat seal layer can be strongly adhered, and the laminate strength can be increased.

  Examples of the filler constituting the primer composition include calcium carbonate, barium sulfate, alumina white, silica, talc, glass frit, and resin powder. When a filler is blended, the viscosity of the solution containing the polyurethane resin or polyester resin can be adjusted, the coating suitability can be improved, and a polyurethane resin or polyester resin and a silane coupling agent can be used as a binder resin. Thus, the cohesive strength of the coating film can be improved.

(8) Anchor coat In the present invention, for example, when the heat seal layer is formed by extrusion, the heat seal layer can be formed on the primer layer via the anchor coat. Examples of the anchor coat used include isocyanate (urethane), polyethyleneimine, polybutadiene, organic titanium, and other anchor coating agents. More preferably, for example, aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate, or aliphatic polyisocyanates such as hexamethylene diisocyanate, xylylene diisocyanate, etc. Mainly used are polyether polyurethane resins, polyester polyurethane resins, and polyacrylate polyurethane resins obtained by reacting polyfunctional isocyanates with polyether polyols, polyester polyols, polyacrylate polyols, and other hydroxyl group-containing compounds. Ingredients. According to these, it is possible to form a thin film rich in flexibility and flexibility, improve its tensile elongation, and as a film having flexibility, flexibility, etc. against a barrier thin film layer made of an inorganic oxide Acting, improving processability such as laminating and printing, avoiding the occurrence of cracks in the barrier thin film layer made of inorganic oxide, and tight adhesion between the barrier film and the heat seal layer And the occurrence of cracks in the barrier thin film layer made of an inorganic oxide can be prevented, and the laminate strength can be improved. The anchor coat layer made of the anchor coat preferably has a tensile elongation of 100 to 300% based on JIS standard K7113.

(9) Undercoat As the undercoat, for example, polyester resin, polyamide resin, polyurethane resin, epoxy resin, phenol resin, (meth) acrylic resin, polyvinyl acetate resin, polyethylene or polypropylene A resin composition having a vehicle as a main component of a polyolefin resin such as the above or a copolymer or modified resin thereof, a cellulose resin, or the like can be used.

(10) Plasma treatment In the present invention, the inorganic oxide vapor-deposited film is preferably subjected to a plasma treatment in the surface treatment, whereby a clearer printed layer can be formed.

As the plasma treatment for the inorganic oxide vapor deposition film, an inorganic gas such as oxygen gas, nitrogen gas, argon gas, helium gas can be used as the plasma gas. In particular, oxygen gas or oxygen gas and argon gas can be used. It is preferable to perform plasma treatment using an inorganic gas containing an oxygen gas as a plasma gas, such as the above mixed gas. In addition, it is possible to perform plasma treatment at a lower voltage, so that there is no discoloration of the surface of the inorganic oxide vapor deposition film, and the surface of the inorganic oxide vapor deposition film is subjected to, for example, a chemical reaction or the like. An OH group or the like can be introduced, and further, Si—C bonds existing in the inorganic oxide vapor deposition film can be converted to SiO ₂ . Furthermore, the plasma treatment increases the cross-linking density of the inorganic oxide vapor-deposited film with the gas barrier composition, improves its humidity dependency, and improves the barrier property against water vapor as well as the gas barrier property against oxygen gas. In addition, it is possible to stably maintain a high gas barrier property against oxygen gas, water vapor, etc., and furthermore, a plasma composed of an inorganic gas containing oxygen gas in a vacuum on the surface of the inorganic oxide deposition film. By performing a plasma treatment using a gas to form a plasma treatment layer, a substrate such as a printing layer, an adhesive layer, an anchor coat layer, a heat sealable resin layer, or the like is formed on the plasma treatment layer. In the case of laminating, it is possible to improve the tight adhesion and the like and remarkably increase the lamination strength.

Specifically, it is desirable to use a mixed gas of oxygen gas and argon gas, and the gas pressure of the mixed gas of oxygen gas and argon gas is about 1 × 10 ^{−1 to} 10 −10 Torr, More preferably, the 1 × 10 ⁻² to 1 × 10 ⁻⁸ Torr position is desirable, and the ratio of oxygen gas to argon gas is oxygen gas: argon gas = 100: 0 to 30:70 in terms of partial pressure ratio. More preferably, the 90:10 to 70:30 position is desirable, and the plasma output is preferably about 100 to 2500 W, more preferably about 500 to 1500 W, and the processing speed is 100 ˜600 m / min, more preferably 200 to 500 m / min. When the partial pressure ratio between the oxygen gas and the argon gas is increased, if the argon gas partial pressure is increased, oxygen molecules activated by the plasma are reduced, the argon gas acts as a reducing gas, and the introduction of hydroxyl groups is inhibited. Is not preferable. In addition, when the plasma output is less than 100 W, more preferably less than 500 W, the activation of oxygen gas is lowered, and it is difficult to produce highly active oxygen atoms. Furthermore, if it exceeds 2500 W, the plasma output is too high, which is not preferable because it causes a problem that the physical properties of the deposited film deteriorate due to deterioration of the deposited inorganic oxide film or the like.

  Further, when the above processing speed is less than 100 m / min, further less than 250 m / min, the amount of oxygen plasma is small, and when it exceeds 600 m / min, and further exceeds 500 m / min, it is inorganic. Oxidation of the oxide vapor deposition film proceeds rapidly and the transparency becomes high, but the barrier property is lowered, which is not preferable.

  In the present invention, in plasma processing, plasma is generated by using three types of devices such as direct current glow discharge, radio frequency (AF) discharge, and microwave discharge. Can do. In the present invention, a high frequency (AF) discharge device of 3.56 MHz can be used.

(11) Heat-seal layer As the heat-seal layer, polyolefin resins having various heat-seal properties that can be melted by heat and fused to each other can be used. Specifically, low density polyethylene, medium density polyethylene, high density polyethylene, linear (linear) low density polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-acrylic acid copolymer, ethylene -Ethyl acrylate copolymer, ethylene-methacrylic acid copolymer, ethylene-α / olefin copolymer polymerized using metallocene catalyst, polypropylene, ethylene-methyl methacrylate copolymer, ethylene-propylene copolymer Polyolefin resins such as methylpentene polymer, polybutene polymer, polyethylene or polypropylene modified with an unsaturated carboxylic acid such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, Vinyl acetate Resins, poly (meth) acrylic resin, one or more films made of a resin such as polyvinyl chloride resin or sheet or coated film and the like can be used.

  The heat seal layer may be previously laminated with another layer using a film, or the resin constituting the heat seal layer may be melt extruded and laminated with the other layer.

  The heat seal layer may be a single layer or a multilayer composed of one of the above resins, and the thickness of the heat seal layer is 15 to 130 μm, more preferably 20 to 80 μm.

(12) Intermediate base material In the present invention, instead of the plastic base material film or together with the plastic base material film, an auxiliary material for the seed wrapping material between the inorganic oxide vapor-deposited film and the heat seal layer, the machine An intermediate substrate having excellent mechanical, physical and chemical strengths may be provided. Thereby, heat resistance, moisture resistance, pinhole resistance, puncture resistance, etc. can be improved. As such an intermediate substrate, for example, one or more of a polyester resin, a polyamide resin, a polyaramid resin, a polypropylene resin, a polycarbonate resin, a polyacetal resin, a fluorine resin, and the like can be suitably used. In the present invention, the plastic substrate film may be any of an unstretched film of the resin and a film stretched in a uniaxial direction or a biaxial direction. In the present invention, it is particularly preferable to use a stretched nylon film, a biaxially stretched polyethylene terephthalate film or a biaxially stretched polypropylene film.

  In the present invention, the thickness of the intermediate substrate is not particularly limited as long as strength, puncture resistance, rigidity and the like can be ensured, but it is preferably 6 to 100 μm, more preferably 9 to 50 μm.

(13) Adhesive for laminating In the present invention, the adhesive between the plastic base film and the inorganic oxide vapor-deposited laminated film, the adhesion between the inorganic oxide vapor-deposited laminated film and the heat seal layer, or the intermediate between the inorganic oxide vapor-deposited laminated film and the intermediate film. Adhesion with the base material, and adhesion between the intermediate base material and the heat seal layer can be performed via a laminating adhesive.

  The adhesive for laminating comprises a polyvinyl acetate adhesive, a homopolymer such as ethyl acrylate, butyl, 2-ethylhexyl ester or a copolymer of these with methyl methacrylate, acrylonitrile, styrene, etc. Polyacrylate adhesives, cyanoacrylate adhesives, ethylene copolymer adhesives made of copolymers of ethylene and monomers such as vinyl acetate, ethyl acrylate, acrylic acid, methacrylic acid, etc., cellulose adhesives Polyester adhesive, polyamide adhesive, polyimide adhesive, amino resin adhesive made of urea resin or melamine resin, phenol resin adhesive, epoxy adhesive, polyurethane adhesive, reactive type (meta ) Acrylic acid adhesive, chloroprene rubber, nitrile Beam, styrene - inorganic adhesive made of butadiene rubber, a silicone-based adhesive, an alkali metal silicate, inorganic adhesive made of low-melting glass, it is possible to use other adhesives.

  More preferably, for example, aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate, or aliphatic polyisocyanates such as hexamethylene diisocyanate, xylylene diisocyanate, etc. Mainly used are polyether polyurethane resins, polyester polyurethane resins, and polyacrylate polyurethane resins obtained by reacting polyfunctional isocyanates with polyether polyols, polyester polyols, polyacrylate polyols, and other hydroxyl group-containing compounds. Ingredients. According to these, it is possible to form a thin film rich in flexibility and flexibility, improve its tensile elongation, and as a film having flexibility, flexibility, etc. against a barrier thin film layer made of an inorganic oxide It can act and improve processing aptitude, such as lamination processing and printing processing, and can avoid generation of a crack etc. to a barrier thin film layer which consists of inorganic oxides. The laminate adhesive layer made of the above-mentioned laminate adhesive preferably has a tensile elongation of 100 to 300% based on JIS standard K7113.

  The composition system of these adhesives may be any composition form such as an aqueous type, a solution type, an emulsion type, and a dispersion type, and the property may be any of a film, a sheet, a powder, a solid, and the like. Furthermore, the reaction mechanism may be any of a chemical reaction type, a solvent volatilization type, a heat welding type, a hot pressure type, and the like.

Although there is no limitation in the usage-amount of the adhesive agent for lamination, Generally, it is 0.1-10 g / m < ² > (dry state). The laminating adhesive can be applied by roll coating, gravure coating, kiss coating or other coating methods or printing methods.

  In bonding, a laminating adhesive may be applied after performing a surface treatment in advance. For example, a primer is applied to the surface of the inorganic oxide vapor deposition film to form a primer layer, and then a base material such as a heat seal layer is laminated on the surface of the primer layer via a laminating adhesive using a dry lamination lamination method. can do.

(14) Manufacturing method of seed packaging material The seed packaging material of the present invention is an inorganic oxide vapor deposition laminated film in which an inorganic oxide vapor deposition film (23) is provided in advance on one surface of a base film layer (21). Adhesive for laminating is appropriately performed so that the heat-seal layer is the innermost layer in which one or more of a plastic base film, an inorganic oxide vapor deposition film, and an intermediate base is formed in advance. It can be manufactured by bonding through an agent layer. The film may be any film such as extrusion film formation, inflation film formation, and coating film. Moreover, when the said inorganic oxide vapor deposition laminated | multilayer film is marketed, a commercial item can also be used.

  The printed layer may be printed directly on one or more of a plastic substrate film, an inorganic oxide vapor deposition film, and an intermediate substrate in order of dark to light color, but preferably a plastic substrate film and an inorganic oxide vapor deposition. It is preferable to perform surface treatment such as corona treatment or plasma treatment on the film or intermediate substrate, or after applying a primer to form a primer layer. As a result, a clear printed layer can be formed. In the present invention, the uppermost layer of the printed layer is light, particularly preferably white, and this white printed layer is a base film of a heat seal layer, an intermediate substrate, and an inorganic oxide vapor-deposited laminated film via an adhesive for lamination. Laminated with any of the layers.

  Further, in the present invention, when any film or layer is laminated, if necessary, pretreatment such as corona treatment or ozone treatment can be applied to the film as described above. (Urethane-based), polyethyleneimine-based, polybutadiene-based, organic titanium-based anchor coating agents, or polyurethane-based, polyacrylic-based, polyester-based, epoxy-based, polyvinyl acetate-based, cellulose-based and other adhesives for laminates In addition to a known pretreatment such as, an anchor coat can be used.

(15) Seed Bag The seed bag of the present invention can be manufactured by stacking the heat-sealing layers of the seed packaging material so as to face each other and heat-sealing the end in a bag shape. In the present invention, when the uppermost layer of the print layer is printed with a light color ink such as a white ink, the light color ink layer such as the uppermost white ink can be visually observed from the heat seal layer.

  Since the seed wrapping material has a window opening in the printed layer, a window opening having a white reflection density of 0.1 to 0.3 is formed in any of the seed bags. In the present invention, there is no limitation on the location where the window opening portion is formed. For example, as shown in FIG. 2, the window opening portion (120) is formed at the lower part of either the front surface or the back surface of the seed bag (100). Is preferred. The stored contents can be easily confirmed through the window opening (120). In addition, when the transparency of the window opening (120) is adjusted to a specific range with a light color ink such as white ink, printing is performed with dark ink from the outside of the seed bag from above the window opening. This can be done and the printed content can be easily read. As described above, when the uppermost layer of the print layer is printed with light color ink such as white ink, the heat seal layer side is light color such as white, and the background of the window opening portion (120) is It becomes white or light color. For this reason, it is possible to facilitate reading of the printing on the upper surface of the window opening portion (120).

  In general, information common to seeds such as a trade name, information about stored seeds and a cultivation method is often printed on the seed bag. Such printing can be performed conventionally on the outer periphery (125) of FIG. On the other hand, in the seed bag of the present invention, the contents can be confirmed with the naked eye by providing the window opening portion (120), and the upper surface of the window opening portion (120) is different from the seed bag body. Printing can be performed. Examples of the contents printed on the window opening part (120) include individual information such as a lot number, a manufacturing date, a quality retention period, a production place, and a germination rate.

  In the present invention, the seed bag of the present invention can be produced by various methods depending on the position of the window opening portion of the seed packaging material. For example, when using a seed wrapping material having the plastic base film (10) of the present invention in the outermost layer and having the heat seal layer (30) in the innermost layer, for example, as shown in FIG. 120) is positioned at the lower part of either the front or back surface of the seed bag, folded back into a bag shape so that the heat seal layer (30) of the seed wrapping material faces, and the two separated sides are overlapped There is a method of heat-sealing the side and the bottom.

  Moreover, in this invention, the window opening part (120) should just be provided in the seed bag (100) at least one place. Therefore, for example, the seed wrapping material of the present invention is used so that the window opening portion is formed on either the front surface or the back surface of the seed bag, and the seed wrapping material window of the present invention is formed on the other surface. It is preferable to use a portion having no perforated portion. Moreover, when forming a several window opening part (120), what is necessary is just to make it a window opening part not overlap when manufacturing the bag for seeds.

  In addition, the heat seal layer located in the innermost layer of the seed wrapping material is faced and overlapped, and thereafter, the heat seal part is formed by heat-sealing the three sides of the outer periphery and the upper part thereof. By forming the opening, a three-side sealed type seed bag can be manufactured. If these seed bags are used, various seeds are filled from the upper opening, and then the opening is heat-sealed, a packaged product using the seed bag of the present invention can be manufactured. it can. In addition, as the shape of the seed bag of the present invention, a packaging bag having various forms suitable for the contents such as a pillow packaging form, a gusset packaging form, a standing (self-supporting) pouch packaging form, and the like can be manufactured. . In addition, as a method of heat sealing, it can carry out by well-known methods, such as a bar seal, a rotary roll seal, a belt seal, an impulse seal, a high frequency seal, an ultrasonic seal, for example.

  In addition, the seed bag of the present invention may be provided with cuts (115) so that the corners (113) of the four corners are cut into round shapes and can be easily opened as shown in FIG. Such incision can be appropriately selected in consideration of the stretching direction of the plastic substrate film to be used.

  Examples of seeds that can be stored in the seed bag of the present invention include vegetables, flower seeds, and other fruits.

  EXAMPLES Next, although an Example is given and this invention is demonstrated concretely, these Examples do not restrict | limit this invention at all.

Example 1
A normal gravure ink composition was used for the corona treatment layer of a 40 μm thick biaxially stretched polypropylene film (OPP film) (trade name “P2161” manufactured by Toyobo Co., Ltd.), and printing was performed by a gravure printing method. . Printing starts on the corona-treated layer from dark to light, in black, indigo, red, yellow, and white. Except for white, a rectangular window with a length of 27 mm and a width of 63 mm can be formed. except printed on (the outer peripheral portion), white line number of the gravure direct plate over the entire surface, plate depth, the setting of the knitted seat, window perforated portion becomes thin white translucent, to form a printed layer.

  On the printed layer, a two-component curing adhesive for lamination (manufactured by Mitsui Takeda Chemical Co., Ltd., trade name “main agent A969 / hardening agent A5”) is coated by the gravure roll coating method, and this adhesive layer for lamination is applied. The surface of the barrier coating film of the silica vapor deposited PET film (Dai Nippon Printing Co., Ltd., trade name “IB-PET (silica)”) is overlaid, and both are laminated by dry lamination. The polyethylene terephthalate surface of the barrier film of the film is coated with a two-component curable adhesive for laminate (manufactured by Mitsui Takeda Chemical Co., Ltd., trade name “main agent A969 / curing agent A5”) by the gravure roll coating method. A 60 μm thick polyethylene film (“LC-21” manufactured by Tamapoly Co., Ltd.) We combined the two laminated by dry lamination to produce a seed for packaging material of the present invention.

  The layer structure of the obtained seed packaging material is: OPP film 40 μm / pattern printing + translucent window opening printing layer 1 μm / dry laminate adhesive layer 3 μm / IB-PET (silica) film 60 μm.

  The reflection density, haze, total light transmittance, oxygen permeability, and water vapor permeability of the seed packaging material were measured. The results are shown in Tables 1-3.

  As shown in FIG. 6, the seed wrapping material produced above is overlapped in a bag shape so that the surface of the polyethylene terephthalate film as the heat-sealable resin layer located in the innermost layer faces, and then A seed bag of 98 mm × 155 mm with a three-side seal was manufactured by heat-sealing with a seal width of 7 mm except for the opening at the end around the outer periphery. Subsequently, the lot number and germination rate were printed from the outside on the window opening of the seed bag. Seeds were filled from the opening of the seed bag on which the lot number and germination rate were printed, and the opening was heat sealed to produce a seed filling bag.

  Moreover, the said seed filling bag was observed from the external appearance.

  In the seed filling bag of Example 1, seeds were difficult to see in the pattern printing part (125 in FIG. 2), and the shape and color of the seed could be confirmed in the window opening part (120 in FIG. 2). On the other hand, the lot number printed on the window opening and the germination rate could be visually read from the outside.

Example 2
Printing is carried out by a gravure printing method using a normal gravure ink composition on a corona-treated layer of a biaxially stretched polypropylene film (OPP film: Toyobo Co., Ltd., trade name “P2161”) having a thickness of 40 μm. It was. Printing starts on the corona-treated layer from dark to light, in black, indigo, red, yellow, and white. Except for white, a rectangular window with a length of 27 mm and a width of 63 mm can be formed. except printed on (the outer peripheral portion), white line number of the gravure direct plate over the entire surface, plate depth, the setting of the knitted seat, window perforated portion becomes thin white translucent, to form a printed layer.

  On the printed layer, a two-component curing adhesive for lamination (manufactured by Mitsui Takeda Chemical Co., Ltd., trade name “main agent A969 / hardening agent A5”) is coated by the gravure roll coating method, and this adhesive layer for lamination is applied. , Alumina-deposited PET film (Dai Nippon Printing Co., Ltd., trade name “IB-PET (alumina)”) is coated with the barrier coating film and laminated by dry lamination. The polyethylene terephthalate surface of the barrier film of the film is coated with a two-component curable adhesive for laminate (manufactured by Mitsui Takeda Chemical Co., Ltd., trade name “main agent A969 / curing agent A5”) by the gravure roll coating method. 60 μm thick polyethylene film (“LC-21” manufactured by Tamapoly Co., Ltd.) Superposition, both laminated by dry lamination to produce a seed for packaging material of the present invention.

  The layer structure of the obtained seed packaging material was OPP film 40 μm / pattern printing + translucent window opening printing layer 1 μm / dry laminate adhesive layer 3 μm / IB-PET (alumina) film 12 μm / dry laminate adhesive layer 3 μm / polyethylene. The film is 60 μm.

  The reflection density, haze, total light transmittance, oxygen permeability, and water vapor permeability of the seed packaging material were measured. The results are shown in Tables 1-4.

Example 3
On the surface of the barrier coating film of a silica-deposited PET film (Dai Nippon Printing Co., Ltd., trade name “IB-PET (silica)”), printing was performed by a gravure printing method using a normal gravure ink composition. . Printing starts on the corona-treated layer from dark to light, in black, indigo, red, yellow, and white. Except for white, a rectangular window with a length of 27 mm and a width of 63 mm can be formed. except printed on (the outer peripheral portion), white line number of the gravure direct plate over the entire surface, plate depth, the setting of the knitted seat, window perforated portion becomes thin white translucent, to form a printed layer.

  On the printed layer, a two-component curing adhesive for lamination (manufactured by Mitsui Takeda Chemical Co., Ltd., trade name “main agent A969 / hardening agent A5”) is coated by the gravure roll coating method, and this adhesive layer for lamination is applied. A 20 μm-thick OPP film (trade name “U-2”, manufactured by Tosero Co., Ltd.) is overlaid, and both are laminated by dry lamination. An adhesive for laminating (made by Mitsui Takeda Chemical Co., Ltd., trade name “main agent A969 / curing agent A5”) was coated by a gravure roll coating method, and a polyethylene film (Tamapoly Co., Ltd.) having a thickness of 60 μm was coated on the laminating adhesive layer. "LC-21" manufactured by the company was superposed, both were dry laminated and laminated to produce the seed packaging material of the present invention.

  The layer structure of the obtained seed packaging material was IB-PET (silica) film 12 μm / pattern printing + translucent window opening printing layer 1 μm / dry laminate adhesive layer 3 μm / OPP film 20 μm / dry laminate adhesive layer 3 μm / polyethylene. The film is 60 μm.

  The reflection density, haze, total light transmittance, oxygen permeability, and water vapor permeability of the seed packaging material were measured. The results are shown in Tables 1-4.

Example 4
On the surface of the barrier coating film of alumina-deposited PET film (Dai Nippon Printing Co., Ltd., trade name “IB-PET (alumina)”), printing was performed by a gravure printing method using a normal gravure ink composition. . Printing starts on the corona-treated layer from dark to light, in black, indigo, red, yellow, and white. Except for white, a rectangular window with a length of 27 mm and a width of 63 mm can be formed. except printed on (the outer peripheral portion), white line number of the gravure direct plate over the entire surface, plate depth, the setting of the knitted seat, window perforated portion becomes thin white translucent, to form a printed layer.

  On the printed layer, a two-component curing adhesive for lamination (manufactured by Mitsui Takeda Chemical Co., Ltd., trade name “main agent A969 / hardening agent A5”) is coated by the gravure roll coating method, and this adhesive layer for lamination is applied. A 20 μm-thick OPP film (trade name “U-2”, manufactured by Tosero Co., Ltd.) is overlaid, and both are laminated by dry lamination. An adhesive for laminating (made by Mitsui Takeda Chemical Co., Ltd., trade name “main agent A969 / curing agent A5”) was coated by a gravure roll coating method, and a polyethylene film (Tamapoly Co., Ltd.) having a thickness of 60 μm was coated on the laminating adhesive layer. "LC-21" manufactured by the company was superposed, both were dry laminated and laminated to produce the seed packaging material of the present invention.

  The layer composition of the obtained seed packaging material was IB-PET (alumina) film 12 μm / pattern printing + translucent window opening printing layer 1 μm / dry laminate adhesive layer 3 μm / OPP film 20 μm / dry laminate adhesive layer 3 μm / polyethylene. The film is 60 μm.

  The reflection density, haze, total light transmittance, oxygen permeability, and water vapor permeability of the seed packaging material were measured. The results are shown in Tables 1-4.

なお、反射濃度、ヘーズ、全光線透過率、酸素透過度、水蒸気透過度は、以下の方法で測定した。

The reflection density, haze, total light transmittance, oxygen permeability, and water vapor permeability were measured by the following methods.

(I) Reflection density About the outer peripheral part and window opening part of the printing layer of the seed packaging material, it measured using the reflection densitometer (ATECH LTD company make, X-RITE model 810).

(Ii) Haze The haze meter (110M-2K manufactured by Suga Test Instruments Co., Ltd.) was used to measure the outer periphery and window opening of the printed layer of the seed packaging material.

(Iii) Total light transmittance About the outer peripheral part and window opening part of the printing layer of the seed packaging material, it measured using the total light transmittance measuring machine (110M-2K by Suga Test Instruments).

(Iv) Oxygen permeability With respect to the seed wrapping material, using a measuring instrument manufactured by MOCON, USA (model name: OX-TRAN 2/20) under the conditions of a temperature of 23 ° C. and a humidity of 90% RH It was measured.

(V) Water vapor transmission rate For seed packaging material, using a measuring instrument manufactured by MOCON, USA (model name: Permatran 3/31) under conditions of a temperature of 40 ° C. and a humidity of 90% RH It was measured.

  Since the seed packaging according to the present invention is provided with a window opening in the printed layer, the contents can be observed from the outside, and the window opening can be printed from outside, Individual information such as lots can be printed, which is excellent in aesthetics, functional and useful.

FIG. 1 (a), (b) is a cross-sectional view illustrating the seed wrapping material used in the present invention. It is a figure which shows the external appearance of the bag for seeds used by this invention. It is a cross-sectional view of a plastic substrate film having a printed layer in the seed packaging material of the present invention, and is a diagram for explaining a method of forming a printed layer having a window opening on the plastic substrate film. 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. It is explanatory drawing at the time of manufacturing a seed bag using the packaging material for seeds of this invention.

Explanation of symbols

10 ... plastic base film,
20 ... Inorganic oxide vapor-deposited laminated film,
21 ... Base film layer,
23 ... Inorganic oxide vapor deposition layer,
30 ... heat seal layer,
40 ... intermediate substrate,
50 ... printing layer,
57 ... outer periphery,
58 ... Window opening,
60 ... Primer layer,
70 ... Laminate adhesive layer,
80 ... corona treatment layer,
100 ... Seed wrapping material,
110 ... heat seal part,
113 ... corner,
115 ... notches,
120 ... Window opening,
125 ... outer peripheral part.

Claims (6)

From the outer surface side, at least a plastic base film, a printed layer, an inorganic oxide vapor-deposited laminated film, and a heat sealing layer are sequentially laminated,
The seed wrapping material has a window opening ,
The printed layer on the outer peripheral portion other than the window opening is printed with white ink on the entire surface, and the white ink is located on the innermost surface of the printed layer,
The printed layer of the window opening is made of white ink,
And the window opening part has a white reflection density of 0.1 to 0.3,
The said inorganic oxide vapor deposition laminated | multilayer film is a laminated film which provided the inorganic oxide vapor deposition film in one surface of the base film layer, The seed packaging material characterized by the above-mentioned. From the outer surface side, at least an inorganic oxide vapor-deposited laminated film, a printed layer, an intermediate substrate and a heat sealing layer are sequentially laminated for seeds,
The seed wrapping material has a window opening,
The printed layer on the outer peripheral portion other than the window opening is printed with white ink on the entire surface, and the white ink is located on the innermost surface of the printed layer,
The printed layer of the window opening is made of white ink,
And the window opening part has a white reflection density of 0.1 to 0.3,
The said inorganic oxide vapor deposition laminated | multilayer film is a laminated film which provided the inorganic oxide vapor deposition film in one surface of the base film layer, The seed packaging material characterized by the above-mentioned . The seed packaging material according to claim 1 , wherein a printed layer is further printed on an outer surface of the window opening portion of the seed packaging material. The printing layer on the outer peripheral portion of the seed wrapping material other than the window opening portion is printed in the order of black ink, indigo ink, red ink, yellow ink, and white ink from the outer surface side. Item 4. A seed packaging material according to any one of Items 1 to 3 . The intermediate substrate wherein the plastic base film or is, stretched nylon film, a biaxially stretched polyethylene terephthalate film or a biaxially oriented polypropylene film, characterized in that it is a thick 6～100Myuemu, claim 1 seed child for packaging material according to any one of the 4. A seed bag formed by molding the seed packaging material according to any one of claims 1 to 5 into a bag shape.

Images