JP4730189B2 - Packaging materials and packaging containers for nutrients using the same - Google Patents

Description

  The present invention relates to a packaging material and a nutrient packaging container using the packaging material. More specifically, the present invention has excellent moisture proofing properties, storage stability, and content visibility. For example, when used as a packaging material for a packaging container for nutrients, steam retort sterilization treatment after filling the content Each layer does not peel even by heating and pressure sterilization treatment with water vapor, etc., and the contents can be stored for a long period of time, and the packaging material that makes it possible to accurately adjust the dosage and administration rate, and It is related with the packaging container for used nutrients.

  Nutrients can be used either orally after a surgery, or for humans who are difficult to ingest nutrients using a normal oral diet (hereinafter simply referred to as “users”), or by nasal tube, gastrostomy or intestinal fistula. In order to supply to the stomach, duodenum or jejunum, the necessary nutrients are adjusted to a low viscosity. Generally, nutrients contain semi-digested proteins, carbohydrates, etc. as components, and these components are denatured and decomposed by gases such as oxygen and water vapor and light in the ultraviolet to visible short wavelength region. It is known to be easy. Therefore, the packaging container for nutrients is required to have both excellent gas barrier properties and light shielding properties in order to maintain the quality and the like.

  In addition, the nutrients described above are usually high in packaging containers filled with nutrients because they are heated and pressurized and sterilized with water vapor so that the contents are not denatured or decomposed after the packaging containers are filled. Moisture resistance is required.

  Furthermore, in administration of nutrients, it is necessary to adjust the dose and administration rate according to the age, weight and symptoms of the user. Therefore, in order to administer an appropriate amount of nutrient at an appropriate rate, it is desirable to provide means for checking the remaining amount of contents in the packaging container.

  Conventionally, various materials such as aluminum foil and aluminum vapor deposition film have been developed and proposed as packaging materials for the nutrients. A packaging material using such an aluminum foil is excellent in light shielding properties and gas barrier properties, but has a problem that it is inferior in incineration and is not easily disposed of after use. Furthermore, since the above packaging material does not transmit light at all, the remaining amount of the contents cannot be confirmed, and the dosage and the administration rate cannot be adjusted accurately.

  In addition, as a laminated material used as a packaging container for medicines and foods and drinks, Patent Document 1 discloses that any one of “a laminated material in which at least a base film layer and a heat seal layer are laminated, and further constituting the laminated material” The light-shielding laminated material characterized in that a continuous printing film made of printing ink is provided in such a layer. Although the light-shielding laminated material described in Patent Document 1 has both gas barrier properties and light shielding properties and has good storage stability, the total light transmittance is adjusted to 0.0 to 0.2% over the entire laminated material. Therefore, the remaining amount of contents cannot be confirmed. Therefore, when these are used as packaging materials for nutrients, there arises a problem that the dose and the administration rate cannot be accurately adjusted. Furthermore, in the laminated material described in Patent Document 1, when a resin film on which an inorganic oxide is vapor-deposited is used as an intermediate layer and a printed layer is formed on the inorganic oxide vapor-deposited film, the component that forms the printed layer is an inorganic oxide. It infiltrates into a vapor deposition film, the adhesiveness of an inorganic oxide vapor deposition film and a resin film, ie, moisture resistance, falls, and an inorganic oxide will peel from a resin film by a retort and boil process.

Further, Patent Document 2 states that “a chromatic color ink containing a white pigment and a black pigment, wherein the black pigment is 3 to 5 parts by mass in 100 parts by mass of all pigments of the chromatic ink. Describes a packaging material characterized in that a chromatic ink layer made of ink is provided on a light-shielding printing layer. The packaging material described in Patent Document 2 also has good storage stability, but the light transmittance in the wavelength region of 300 nm to 800 nm is adjusted to 10% or less over the entire packaging material. The remaining amount of cannot be confirmed. Therefore, when these are used as packaging materials for nutrients, there arises a problem that the dose and the administration rate cannot be accurately adjusted. Furthermore, in the packaging material described in Patent Document 2, when a resin film on which an inorganic oxide is vapor-deposited is used as a base film layer and a printed layer is formed on the inorganic oxide vapor-deposited film, the component that forms the printed layer is inorganic. Infiltrating into the oxide vapor deposition film, adhesion between the inorganic oxide and the resin film, that is, moisture resistance is lowered, and the inorganic oxide is peeled off from the resin film by retort and boil treatment.
Japanese Patent Laid-Open No. 10-305513 International Publication No. 2004/020303 Pamphlet

  As described above, a variety of packaging materials for medicines and foods and drinks with excellent contents preservability are known, but none of the packaging materials have the contents visibility at all and are not moisture-proof. It is enough.

  On the other hand, the present invention has all of excellent moisture proofing, storage stability and contents visibility. For example, when used as a packaging container for nutrients, heating with steam such as steam retort sterilization after filling the contents.・ Providing a packaging material that does not peel off each layer even under pressure sterilization treatment, allows the content to be stored for a long period of time, and enables the dosage and rate of the content to be adjusted accurately. .

As a result of diligent research to solve the above-mentioned problems, the present inventors have found that the protein and carbohydrate that are the contents are mainly destroyed by light in a specific wavelength region of ultraviolet to visible short wavelength region, and the printed layer When components infiltrate a gas barrier layer such as an inorganic oxide vapor-deposited film by heating / pressure sterilization treatment with water vapor, the adhesion between the inorganic oxide and the resin film that supports it decreases, and the inorganic oxide Focusing on peeling from the resin film, a part or all of the packaging material having gas barrier properties should be shielded only from light in the specific wavelength region, and a specific surface of the layer constituting the packaging material By providing a printed layer, it was found that a packaging material excellent in all of storability, contents visibility and moisture resistance, which could not be obtained in the past, was obtained, and the present invention was completed. .
That is, this invention includes the invention shown to the following (a)-(d).
(A) In a packaging material made of a laminate having at least a base material layer made of a resin film, an intermediate layer made of a resin film, a printing layer, and a heat-sealable resin layer,
A gas barrier layer is provided on one or both surfaces of the base material layer and the intermediate layer,
The printed layer is provided so as not to contact the gas barrier layer, and further, part or all of the packaging material is 20% or less in a wavelength region of 250 nm to 550 nm, and the transmittance further shifts to a longer wavelength region. A packaging material characterized in that it is a content-viewing part that rises and has a light transmittance of 50% or more in the wavelength region of 650 nm to 800 nm, and the other part has a total light transmittance of 20% or less.
(B) The pigment used for the printed layer in the contents visually recognizing portion is selected from the group consisting of amber pigments, yellow pigments, and a mixture of amber pigments or yellow pigments and red pigments The packaging material according to (a), which is a seed or more pigment.
(C) One side of the printing layer is in contact with the base material layer, the intermediate layer, or the heat sealable resin layer, and the other side is another base material layer, the intermediate layer, or the heat sealability. The packaging material according to (a) or (b), which is provided so as to be in contact with any one of the resin layers via an adhesive layer.
(D) The packaging material according to any one of (a) to (c), wherein a printing layer is provided on the base material layer.
(E) The packaging material according to any one of (a) to (d), wherein the gas barrier layer is a vapor-deposited film of an inorganic oxide.
(F) The gas barrier layer comprises a vapor-deposited film of an inorganic oxide and a general formula R ¹ _n M (OR ² ) _m (wherein M represents a metal atom, and R ¹ and R ² have 1 to 8 carbon atoms) Represents an organic group, n is an integer of 0 or more, m is an integer of 1 or more, and n + m represents a valence of M), at least one alkoxide, polyvinyl alcohol, and / or ethylene (A) to (a) comprising a hydrolyzate of alkoxide obtained by polycondensation of a composition comprising vinyl alcohol by a sol-gel method or a gas barrier coating film which is a hydrolyzed condensate of alkoxide The packaging material according to any one of d).
(G) A packaging container for a nutrient using the packaging material according to any one of (a) to (f), the heat-sealable resin layer side of one packaging laminate, and the other packaging A packaging container, wherein the laminated material is overlapped so as to face the heat-sealable resin layer side and the end thereof is heat-sealed.

  The packaging material of the present invention has an excellent gas barrier property, and part or all of the packaging material blocks only light in a specific wavelength region such as an ultraviolet to visible short wavelength region that is involved in denaturation / decomposition of proteins and carbohydrates. Since it transmits light in other wavelength regions, it has excellent storage stability and content visibility. Furthermore, in the packaging material of the present invention, since the printing layer is provided so as not to contact the gas barrier layer, the constituent components of the printing layer constitute the gas barrier layer even if the heating / pressure sterilization treatment with water vapor is performed. As a result, a packaging material excellent in adhesion between the inorganic oxide and the resin film that supports the inorganic oxide can be obtained. That is, according to the present invention, it is excellent in moisture resistance and quality retention characteristics required as a packaging container for medicines and foods and drinks, and can be accurately adjusted in dosage and administration speed, and is particularly suitable for a nutritional packaging container. Packaging material can be obtained.

Hereinafter, the present invention will be described in more detail with reference to the drawings.
1. Configuration of packaging material of the present invention and packaging container using the same (1) Configuration of packaging material of the present invention A specific example of the configuration of the packaging material of the present invention will be described with reference to the drawings. FIG. 1 is a schematic plan view illustrating an example of the appearance of the packaging material of the present invention, and FIGS. 2 to 6 are schematic cross-sectional views illustrating an example of the layer configuration of the packaging material of the present invention.
For example, as shown in FIG. 1, the packaging material A of the present invention may include a packaging material A composed of a content visual recognition part 1 and another part 2. Here, the content visually recognizing part has a light transmittance of 20% or less in the wavelength region of 250 nm to 550 nm so that light in the ultraviolet to visible short wavelength region involved in the denaturation / decomposition of proteins and carbohydrates can be sufficiently shielded. And preferably 15% or less, particularly 10% or less. When deviating from the above range, contents such as proteins and carbohydrates are denatured and decomposed by light in the ultraviolet to visible short wavelength region, resulting in a problem that storage stability is lowered. Furthermore, the content viewing portion needs to have a light transmittance of 50% or more in the wavelength region of 650 nm to 800 nm so that the remaining amount of the content can be confirmed, preferably 70% or more, particularly 80% or more. It is desirable to be. If it deviates from the above range, it becomes difficult to confirm the remaining amount of the contents. For example, when used as a packaging container for nutrients, there arises a problem that the dose and the administration rate cannot be adjusted accurately. The light transmittance in the wavelength region of 550 nm to 650 nm is not particularly limited and may be anywhere from 0% to 100%, but usually the transmittance gradually increases from 550 nm and becomes 50% or more at 650 nm.
In addition, the other portions need to have a total light transmittance of 20% or less, preferably 10% or less, so as not to affect the storage stability of the contents.

  The packaging material shown in FIG. 1 has a content visually recognizing part provided in a part of the packaging material, but the entire packaging material can also be used as a content visually recognizing part. However, from the viewpoint of providing a content visual recognition part for confirming the remaining amount of the content and printing the product name or pattern on the packaging material, that is, from the viewpoint of design, the content visual recognition part should be It is preferable that 5% to 90%, preferably 10 to 30%, of the area is provided, and the remaining part is the other part. Further, the shape of the content viewing portion may be any shape as long as the purpose of confirming the remaining amount of the content can be achieved. As shown in FIG. In addition, for example, a plurality of horizontally long rectangles may be provided in the packaging material, or a plurality of small circular contents viewing portions may be provided.

  Next, the layer structure of the packaging material of the present invention will be described. As a packaging material of the present invention, for example, as shown in FIG. 2, the packaging material is composed of a laminated material in which a base material layer 3, an intermediate layer 5, and a heat sealable resin layer 4 are laminated in order, and the heat sealable resin layer 4 of the intermediate layer 5. The gas barrier layer 6 is provided on the side surface, and the printed layer 7 constituting the contents visualizing portion and other portions are further formed on the surface of the base material layer 3 or the intermediate layer 5 on the base material layer 3 side. The packaging material B which consists of the layer structure which provided the printing layer 8 can be mentioned.

  Further, as the packaging material of the present invention, for example, as shown in FIG. 3, the packaging material is composed of a laminated material in which a base material layer 3, an intermediate layer 5, and a heat-sealable resin layer 4 are sequentially laminated. A gas barrier layer 6 is provided on the surface, and the printed layer 7 constituting the contents visually recognizing portion on the surface of the intermediate layer 5 on the heat sealable resin layer 4 side or the heat sealable resin layer 4 and other portions The packaging material C which consists of the layer structure which provided the printing layer 8 which comprises can be mentioned.

  Further, as the packaging material of the present invention, for example, as shown in FIG. 4, the intermediate layer is composed of a laminated material in which a base material layer 3, an intermediate layer 5, a second intermediate layer 5a, and a heat-sealable resin layer 4 are sequentially laminated. 5 is provided with a gas barrier layer 6 on the surface of the second intermediate layer 5a side, and further, the printed layer constituting the contents visualizing portion on the surface of the base layer 3 or the base layer 3 side of the intermediate layer 5 7 and a packaging material D having a layer structure provided with a printing layer 8 constituting another part.

Furthermore, as the packaging material of the present invention, as shown in FIG. 5, in the packaging material B shown in FIG. 2, a gas barrier layer 6a is provided between the intermediate layer 5 and the heat-sealable resin layer 4. The packaging material E which consists of a layer structure which provided the intermediate | middle layer 5a of 2 can be mentioned.
Alternatively, as the packaging material of the present invention, as shown in FIG. 6, in the packaging material B shown in FIG. 2, the second heat-sealable resin layer 4a is formed as the outermost layer on the other surface of the base material layer 3. The packaging material F which consists of the laminated layer structure can be mentioned.

  The above illustrations are representative examples of the packaging material of the present invention, and it goes without saying that the present invention is not limited thereto. For example, although not shown in the figure, the printing ink layer may be provided at any position as long as it does not contact the gas barrier layers 6 and 6a. For example, in the packaging container of FIG. You may provide in the heat sealable resin layer 4 side surface of the 2nd intermediate | middle layer 5a, or the heat sealable resin layer 4. FIG. In the present invention, as long as the above conditions are satisfied, the layer structure as a laminated material is designed according to its intended purpose, application, contents to be filled and packaged, its distribution form, sales form, etc. The packaging material of the present invention can be produced by arbitrarily laminating using a gas barrier layer, a heat-sealable resin layer, and other materials.

(2) Configuration of Packaging Container of the Present Invention Next, the packaging container of the present invention formed by bag-making the packaging material of the present invention will be described. FIG. 7 is a schematic perspective view showing the configuration of the packaging container of the present invention formed by bag-making the packaging material shown in FIG. 2, and FIG. 8 is filled with the contents in the packaging container shown in FIG. It is a schematic perspective view which shows the structure of a packaged product. For example, the packaging container G of the present invention shown in FIG. 7 is prepared by preparing two sheets of packaging materials B and B having the layer configuration shown in FIG. 2, and the surfaces of the heat-sealable resin layers 4 and 4 constituting the innermost layer. Can be manufactured by forming the heat seal portions 9, 9 and 9 by heat-sealing the three peripheral edge portions of the packaging materials B and B. The above packaging container is an example, and the present invention is not limited thereby. Similarly, the packaging container of the present invention can be obtained using the packaging materials shown in FIGS. Can be manufactured. Further, the packaging container is provided with the contents visually recognizing parts on both sides. In the present invention, for example, the packaging material B in FIG. 2 and the total light transmittance is 20% or less, that is, only the other parts. It is also possible to heat seal the packaging material made of the above as described above to make a packaging container having a content visually recognizing portion only on one side. Although not shown, in the present invention, various forms can be adopted as the form of the packaging container. As will be described later, for example, a self-supporting bag (standing pouch), a caseette bag, a boat bottom bag, etc. Various forms can be produced. Furthermore, in the present invention, for opening, for example, a notch for opening, a notch or the like can be engraved in a portion corresponding to the opening of the heat seal portion at the peripheral end.

  Next, the packaged product in which the contents are filled and packaged in the packaging container of the present invention as described above will be described. As shown in FIG. 8, the contents are opened from the opening above the packaging container G shown in FIG. 10 and then the upper opening is heat sealed to form the upper seal 11 to produce a packaged product H using the packaging container G of the present invention. In the present invention, as shown in FIG. 8, the packaged product H as described above is opened by holding the opening notches 12, 12 and the like and tearing the bag to open it. Can be taken out and used for purposes that match its contents. Moreover, although not shown in figure, in order to manufacture the packaging container of the nutrient for tube administration using the packaging container of this invention, it is for hanging by arbitrary means, for example in the lower part of the packaging container G shown in said FIG. And a spout may be attached to the packaging container during the heat sealing of the upper opening.

2. Next, in the present invention, in the present invention, the packaging material of the present invention, the base material layer, the intermediate layer, the gas barrier layer, the printing layer, and the like constituting the packaging container, The heat seal resin layer and the like will be described.
(1) Base material layer As the resin film constituting the base material layer provided in the packaging container of the present invention, since this is usually a basic material constituting the packaging material, mechanical, physical, It is desirable to use chemically excellent properties, particularly tough and heat resistant. Specifically, for example, polyester resins, polyamide resins, polyaramid resins, polyolefin resins such as polyethylene or polypropylene, polystyrene resins, polyacrylic or methacrylic resins, polycarbonate resins, polyacetal resins, fluorine resins. A film or sheet of tough resin such as polyacrylonitrile resin or polyvinyl alcohol resin can be used.

  As the resin film or sheet, a stretched film stretched in a uniaxial direction or a biaxial direction in either the longitudinal direction or the transverse direction can be used. As the stretching method, for example, a known method such as a flat method or an inflation method can be used, and a stretching ratio of about 2 to 10 times can be used. The thickness of the film is 5 μm to 100 μm, preferably 10 μm to 50 μm. In the present invention, the resin film as described above is subjected to surface printing or back printing by a normal printing method with a desired printing pattern such as letters, figures, symbols, patterns, patterns, etc. It may be.

(2) Intermediate layer In the present invention, an intermediate layer made of a resin film is provided between the base material layer and the heat-sealable resin layer so as to prevent contact between the printing layer made of printing ink and the gas barrier layer. It is necessary to provide it. By providing the intermediate layer in this way, the adhesion between the base material layer or the intermediate layer and the vapor-deposited film of the inorganic oxide constituting the gas barrier layer is improved, that is, the base material resulting from, for example, retort sterilization treatment It is possible to prevent peeling (delamination) between the layer or the intermediate layer and the vapor-deposited film of the inorganic oxide constituting the gas barrier layer. Further, by providing the intermediate layer, the strength and puncture resistance of the packaging material of the present invention are improved.
The resin film used as the intermediate layer has excellent mechanical, physical, chemical, etc. strength, excellent puncture resistance, etc., heat resistance, moisture resistance, pinhole resistance, transparency It is possible to use a resin film or sheet having excellent properties. Specifically, for example, polyester resin, polyamide resin, polyaramid resin, polypropylene resin, polystyrene resin, polyacrylic or methacrylic resin, polycarbonate resin, polyacetal resin, fluorine resin, polystyrene resin, Polyacrylic or methacrylic resins and other tough resin films or sheets can be used.
As the resin film or sheet, any of an unstretched film or a stretched film stretched in a uniaxial direction or a biaxial direction can be used. Further, 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, etc. If it is too thick, the cost increases and conversely On the other hand, if it is too thin, there arises a problem that strength, puncture resistance and the like deteriorate.

  Furthermore, in the present invention, if necessary, in addition to the above intermediate layer, one or more second, third, etc. intermediate layers made of the above resin film are used as materials constituting the packaging material of the present invention. Can be used. The intermediate layer, the second intermediate layer, the third intermediate layer and the like referred to in the present invention only mean the number of provided intermediate layers, and there is no substantial difference. For example, the packaging material of the present invention In the case where two intermediate layers are provided, when one of them is an intermediate layer, the other is referred to as a second intermediate layer.

(3) Gas barrier layer Since the packaging material of the present invention needs to have an excellent gas barrier property, it has a barrier property against steam, water, etc. on one or both of the base material layer and the intermediate layer. It is necessary to provide a gas barrier layer having Furthermore, as described above, in the packaging material of the present invention, in addition to the base material layer and the intermediate layer, second and third intermediate layers may be provided. In this case, the second and third intermediate layers are provided. A gas barrier layer may be provided. In addition, the gas-barrier base material layer said to this invention means the thing which provided the vapor barrier film mentioned later on the vapor deposition film of an inorganic oxide, and the said vapor deposition film.
Hereinafter, the vapor deposition film of the inorganic oxide constituting the gas barrier layer and the gas barrier coating film will be described.

(A) Inorganic oxide vapor-deposited film In the present invention, examples of the inorganic oxide vapor-deposited film include metal oxides such as silicon oxide (SiO _x ), aluminum oxide, indium oxide, tin oxide, and zirconium oxide. And a mixture of silicon monoxide and silicon dioxide, or a mixture of silicon oxide and aluminum oxide. In the present invention, the vapor-deposited film of the inorganic oxide is formed by, for example, chemical vapor deposition (Chemical Vapor Deposition, CVD, etc.) such as plasma chemical vapor deposition, thermal chemical vapor deposition, or photochemical vapor deposition. ), Or a physical vapor deposition method (Physical Vapor Deposition method, PVD method) such as a vacuum deposition method, a sputtering method, an ion plating method, or an ion cluster beam method. In particular, when a silicon oxide vapor deposition film is formed using chemical vapor deposition, one or two selected from the group consisting of silicon oxide, carbon, hydrogen, silicon, and oxygen. It is possible to vapor-deposit compounds containing chemical compounds or groups consisting of the above elements (hereinafter referred to as “organosilicon oxide”), thereby improving the impact resistance, spreadability, flexibility, etc. of the deposited film. can do. The thickness of the vapor-deposited film of the inorganic oxide is preferably 100 to 3000 mm in order to obtain a sufficient gas barrier property, and particularly preferably 200 to 2000 mm in the present invention. In the above, if the thickness of the inorganic oxide vapor-deposited film exceeds 2000 mm, particularly 3000 mm, the inorganic oxide vapor-deposited film is liable to be cracked, the gas barrier property is lowered, and the material cost is increased. If it is less than 200 mm, or even less than 100 mm, the gas barrier effect cannot be obtained, which is not preferable.

(B) Gas barrier coating film The gas barrier coating film referred to in the present invention is at least one alkoxide represented by the general formula: R ¹ _n M (OR ² ) _m , polyvinyl alcohol and / or ethylene / vinyl alcohol. It means a gas barrier coating film made of a gas barrier composition obtained by polycondensation of a composition containing a sol-gel method.

The alkoxide that can be suitably used in the present invention has a general formula: R ¹ _n M (OR ² ) _m (wherein M is a metal atom, R ¹ and R ² are organic groups having 1 to 8 carbon atoms, and n is 0 or more) , M represents an integer of 1 or more, and n + m represents a valence of M), and at least one kind of a partial hydrolyzate of alkoxide or a hydrolyzed condensate of alkoxide can be used. . In addition, as a partial hydrolyzate of said alkoxide, all the alkoxy groups do not need to be hydrolyzed, The thing by which one or more was hydrolyzed, and its mixture may be sufficient. Further, the hydrolysis condensate represents a dimer or more of a partially hydrolyzed alkoxide, and a 2-6 mer is usually used.

As the metal atom represented by M in the general formula: R ¹ _n M (OR ² ) _m , silicon, zirconium, titanium, aluminum and the like can be used. In the present invention, alkoxysilane in which M is Si is particularly preferable. Moreover, the alkoxide of 2 or more types of different metal atoms can also be mixed and used in the same solution.
In the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m , specific examples of the organic group represented by R ¹ include, for example, a methyl group, an ethyl group, an n-propyl group, i Examples thereof include alkyl groups such as -propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-hexyl group and n-octyl group.
Examples of the alkoxysilane include tetramethoxysilane Si (OCH ₃ ) ₄ , tetraethoxysilane Si (OC ₂ H ₅ ) ₄ , tetrapropoxysilane Si (OC ₃ H ₇ ) ₄ , tetrabutoxysilane Si (OC ₄ H ₉ ). ₄ etc. can be used. These alkoxysilanes may be used alone or in admixture of two or more.

  In the present invention, a silane coupling agent is preferably used in combination with the alkoxide. As the silane coupling agent, a known organic reactive group-containing organoalkoxysilane can be used. Particularly preferred are organoalkoxysilanes having an epoxy group, such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. Can be used. Two or more kinds of such silane coupling agents may be mixed and used, and the amount used is in the range of 0.1 to 20 parts by weight with respect to 100 parts by weight of the alkoxysilane. When 20 parts by weight or more is used, the composite polymer formed is increased in rigidity and brittleness, and the insulation and workability of the composite polymer layer are lowered.

  In the present invention, the composition for forming a gas barrier coating film (coating liquid) contains polyvinyl alcohol and / or ethylene / vinyl alcohol copolymer. By combining polyvinyl alcohol and ethylene / vinyl alcohol copolymer, gas barrier properties, water resistance, weather resistance and the like of the resulting coating film are remarkably improved. Furthermore, a laminated film in which polyvinyl alcohol and ethylene / vinyl alcohol copolymer are combined is excellent in hot water resistance and gas barrier property after hot water treatment in addition to gas barrier properties, water resistance, and weather resistance.

  When the combination of polyvinyl alcohol and ethylene / vinyl alcohol copolymer is employed, the weight ratio of each is preferably 10: 0.05 to 10: 6, more preferably about 10: 1.

The total content of the polyvinyl alcohol and / or ethylene / vinyl alcohol copolymer is in the range of 5 to 600 parts by weight, preferably about 50 to 400 parts by weight, with respect to 100 parts by weight of the total amount of the alkoxide. If it exceeds 600 parts by weight, the brittleness of the composite polymer increases, and the water resistance and weather resistance of the resulting laminated film also deteriorate. When the amount is less than 5 parts by weight, the gas barrier property is lowered.
Specific examples of the polyvinyl alcohol resin include RS-110 (degree of saponification = 99%, degree of polymerization = 1,000) manufactured by Kuraray Co., Ltd., and Kuraray Poval LM-20SO (degree of saponification) manufactured by the same company. = 40%, polymerization degree = 2,000), GOHSENOL NM-14 manufactured by Nippon Synthetic Chemical Industry Co., Ltd. (degree of saponification = 99%, polymerization degree = 1,400), and the like can be used. As a specific example of the ethylene / vinyl alcohol copolymer, a saponified product of a copolymer of ethylene and vinyl acetate, that is, a product obtained by saponifying an ethylene-vinyl acetate random copolymer may be used. it can.

  In this invention, said composition (coating liquid) is apply | coated on a vapor deposition film | membrane, The composition is polycondensed by the sol-gel method, and a coating film is formed. As the sol-gel catalyst, mainly a polycondensation catalyst, a tertiary amine that is substantially insoluble in water and soluble in an organic solvent is used. For example, there are N, N-dimethylbenzylamine, tripropylamine, tributylamine, tripentylamine, and NN-dimethylbenzylamine is particularly preferable. The amount used is 0.01 to 1 part by weight, preferably about 0.03 part by weight, per 100 parts by weight of the total amount of alkoxide and silane coupling agent.

  In the present invention, the above composition may contain an acid instead of the tertiary amine or further. The acid is used as a sol-gel catalyst, mainly as a catalyst for hydrolysis of alkoxides, silane coupling agents and the like. As the acid, mineral acids such as sulfuric acid, hydrochloric acid and nitric acid, and organic acids such as acetic acid and tartaric acid are used. The amount of the acid used is 0.001 to 0.05 mol, preferably about 0.01 mol, based on the total molar amount of the alkoxide and the alkoxide content (for example, silicate moiety) of the silane coupling agent.

  In the present invention, the composition for forming a gas barrier coating film contains 0.1 to 100 moles, preferably 0.8 to 2 moles of water with respect to 1 mole of the total mole amount of alkoxide. Is preferred. Moreover, it is preferable that the composition for gas-barrier coating film formation contains an organic solvent. As the organic solvent, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butanol and the like are used.

The method for forming a gas barrier coating film in the present invention will be described below.
First, an alkoxide such as alkoxysilane, a silane coupling agent, a polyvinyl alcohol resin and / or an ethylene / vinyl alcohol copolymer, a sol-gel method catalyst, water, an organic solvent, and, if necessary, a metal alkoxide Etc. are mixed to prepare a gas barrier coating solution. In the gas barrier coating liquid, the polycondensation reaction gradually proceeds.

  Next, the gas barrier coating solution is applied by a conventional method on an inorganic oxide vapor-deposited film provided on one surface of the substrate, and dried. By the drying, the polycondensation of the alkoxide, metal alkoxide, silane coupling agent, and vinyl alcohol polymer further proceeds to form a composite polymer layer. Preferably, the above operation is repeated to laminate a plurality of composite polymer layers.

  Finally, the film coated with the coating solution is subjected to a temperature of 50 ° C. to 300 ° C., preferably 70 ° C. to 200 ° C. under a normal environment, for 0.005 minutes to 60 minutes, preferably 0.01 minutes. By heating and drying for 10 minutes, condensation is performed, and a gas barrier coating film can be formed.

In the present invention, an ethylene / vinyl alcohol copolymer or a composition using both an ethylene / vinyl alcohol copolymer and polyvinyl alcohol may be used instead of the vinyl alcohol polymer. By using both an ethylene / vinyl alcohol copolymer and polyvinyl alcohol, gas barrier properties after hot water treatment such as boil treatment and retort treatment are further improved.
As a method for applying the gas barrier coating film forming composition, for example, a roll coating such as a gravure coater, a spray coating, a spin coating, a dipping, a brush, a barcode, an applicator or the like is applied once or a plurality of times. With this coating, it is possible to form a gas barrier coating film having a dry film thickness of 0.01 μm to 30 μm, preferably 0.1 μm to 10 μm.
If necessary, when applying the gas barrier composition, a primer agent or the like can be applied on the inorganic oxide vapor-deposited film in advance.

  In the present invention, after a vapor deposition layer and a gas barrier coating film are provided on the resin film, a vapor deposition layer may be further provided, and the gas barrier coating film may be formed on the vapor deposition layer in the same manner as described above. Thus, by increasing the number of stacked layers, the gas barrier property can be further improved.

(2) Print layer The packaging material of the present invention is partly or entirely 20% or less with respect to light in the wavelength region of 250 nm to 550 nm, and further increases in transmittance as it moves to the longer wavelength region, and from 650 nm to A package having such a property, which is a content visualizing portion having a light transmittance of 50% or more with respect to light in the wavelength region of 800 nm, and the rest is another portion having a total light transmittance of 20% or less. The material can be formed by providing a printed layer of a specific printing ink on the contents visualizing part and other parts of the laminated material.
Here, since the printing ink has the property of melting under high temperature and high pressure such as heating and pressure sterilization treatment with steam, when the printing ink is provided in contact with the gas barrier layer, the steam sterilization treatment is performed. The problem is that the constituents of the printing ink infiltrate into the vapor-deposited film of the inorganic oxide constituting the gas barrier layer, which causes the inorganic oxide and the base material layer or intermediate layer supporting it to peel off. Occurs. Therefore, in the present invention, it is necessary that the printing layer made of the specific printing ink is not in contact with the gas barrier layer. Specifically, for example, in the packaging material of the present invention in which a base material layer, an intermediate layer, and a heat-sealable resin layer are sequentially laminated, when the gas barrier layer is provided on the surface of the intermediate layer on the heat-sealable resin layer side The printing layer can be provided on the surface of the base layer or the base layer side of the intermediate layer. Moreover, in the packaging material of the present invention having the above layer structure, when the gas barrier layer is provided on the base material layer, the printed layer is formed on the surface of the intermediate layer on the heat seal resin layer side or on the heat seal resin layer. Can be provided. Further, for example, in the packaging material of the present invention in which a base material layer, an intermediate layer, a second intermediate layer, and a heat-sealable resin layer are sequentially laminated, a gas barrier layer is provided on the surface of the intermediate layer on the second intermediate layer side. In this case, the base layer, the base layer side surface of the intermediate layer, the heat seal resin layer side surface of the second intermediate layer, or any one of the heat seal resin layers, or more Can be provided in a layer.

Hereinafter, the printing ink used for the printing layer which comprises the content visual recognition part in the packaging material of this invention, the printing ink used for the printing layer which comprises another part, and the formation method of a printing layer are demonstrated.
(A) Printing ink used for the printing layer constituting the content viewing portion The printing ink used for the printing layer constituting the content viewing portion is, for example, a binder resin as the main component of the vehicle, and light rays in the wavelength region of 250 nm to 550 nm. A colored ink composition obtained by adding a specific pigment or dye having a light-shielding property, further adding a desired auxiliary agent, and kneading sufficiently with a solvent / diluent or the like can be used.
Examples of pigments having the above properties include yellow pigments such as fast yellow, disazo yellow, titanium yellow, yellow iron oxide, and yellow lead, and amber pigments such as pyrazolone-permanent orange G, cadmium orange, and chrome orange. Mixtures of seeds or more can be used. Furthermore, it is also possible to use a mixture of one or more of the yellow pigments or amber pigments and red pigments such as toluidine red, lake red, bengara, molybdenum red, and vermilion.
Examples of the dye having the above properties include C.I. I. Solvent Yellow 14, C.I. I. Solvent Yellow 56, C.I. I. Yellow dyes such as Acid Yellow, C.I. I. Acid Orange 51, C.I. I. Acid Orange 56, C.I. I. A mixture of one or more amber dyes such as Acid Orange 74 can be used. Further, the above yellow dye or amber dye, and C.I. I. Solvent Red 18, C.I. I. Solvent Red 27, C.I. I. One or more mixtures with red dyes such as Solvent Red 49 can also be used.

  Examples of the binder resin include polyvinyl chloride resin, polyvinyl acetate resin, vinyl chloride-vinyl acetate copolymer, polyacrylic or methacrylic resin, maleic acid resin, fumaric acid resin, and polyacrylonitrile resin. , Polyolefin resin, acid-modified polyolefin resin, polystyrene resin, drying oil alkyd resin, alkyd resin, polyester resin, polyamide resin, polyurethane resin, phenol resin, amino resin, epoxy resin, rosin resin One or a mixture of two or more of resin, ester gum, fiber resin such as nitrocellulose or ethylcellulose, rubber derivative, petroleum resin and the like can be used. Furthermore, as the auxiliary agent, for example, one or more auxiliary agents such as a stabilizer, a plasticizer, an ultraviolet absorber, an antioxidant, a lubricant, an antistatic agent, a filler, waxes, greases, a dispersing agent and the like are used. It can be optionally added and used. Examples of the solvent / diluent include alcohol solvents, ester solvents, ether alcohol solvents, aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, and ketone solvents. In the present invention, using the above materials, for example, premixing using a mixer, kneader, etc., then using a roll mill, ball mill, sand mill, etc. The printing ink to be used can be manufactured. In the present invention, the pigment is added in an amount of 0.1 to 30 parts by weight, preferably 0.4 to 20 parts by weight with respect to 100 parts by weight of binder resin as a vehicle constituting the printing ink. It is desirable to blend.

  Furthermore, in the present invention, as a printing layer constituting the content viewing portion, a printing ink containing a yellow pigment / dye (yellow ink), an amber pigment / dye, or an amber pigment / dye or a yellow pigment / A printing layer can be formed in a single layer using any one of printing inks (amber inks) containing a dye and a red pigment / dye, but light in the wavelength region of 250 nm to 550 nm is more effectively used. In order to shield the light, it is desirable to form a printing layer by laminating two or more layers using one or more of yellow ink or amber ink. In this case, as the printing ink, in addition to the yellow ink and the amber ink, pigments with low light shielding properties such as white pigments such as titanium oxide, zinc white, and zinc sulfide, and printing inks (white inks) containing a white dye. -Printing ink containing dye can also be used, for example, even if a printing layer consisting of two layers of yellow ink and white ink, or a printing layer consisting of three layers of yellow ink, amber ink and white ink is formed. Good.

(B) Printing ink used for printing layer constituting other part When a part of the packaging material of the present invention is a content visually recognizing part, another part having a total light transmittance of 20% or less may be provided. Although necessary, as the printing ink used in such other parts, for example, the binder resin described above is used as the main component of the vehicle, and the total light transmittance of the other parts is 20% or less. A colored ink composition obtained by adding sufficient pigments / dyes, further adding the above-mentioned assistants, solvents / diluents, and kneading them sufficiently can be used.
Examples of the pigment / dye used in the colored ink include the yellow pigment / dye, amber pigment / dye, red pigment / dye, brown pigment, ultramarine blue, bitumen, cobalt titanate green, chromium oxide, etc. Blue to green pigments, white pigments such as titanium oxide, zinc white and zinc sulfide, black pigments such as carbon black, extender pigments such as calcium carbonate, precipitated barium sulfate, clay and talc, azo dyes A pigment, a phthalocyanine pigment, a quinacridone pigment, an isoindolinone pigment, a dioxazine pigment, a thioindigo pigment, a dye / pigment such as an anthraquinone dye / pigment, or a mixture of one or more can be used. In particular, the above black pigment, a mixture of black pigment and white pigment, a mixture of red pigment, green pigment and blue pigment are used. It is preferable to. The amount of the pigment added is 0.1 to 30 parts by weight, preferably 0.4 to 20 parts by weight, based on 100 parts by weight of binder resin as a vehicle constituting the printing ink. desirable.

  Moreover, in this invention, even if it forms a printing layer by one layer using the printing ink containing the said pigment as a printing layer which comprises another part so that a total light transmittance may be 20% or less. Alternatively, the printing layer may be formed of two or more layers using one or more printing inks containing the pigment.

(C) Method for forming printed layer In the present invention, as a method for forming the printed layer, for example, the above-described base material layer, intermediate layer, or heat seal that uses the above-described printing ink and first constitutes the content viewing portion is used. The surface of the layer is printed or coated by the usual printing method or coating method such as gravure coating, roll coating, knife coating, spray coating, gravure printing, flexographic printing, screen printing, offset printing, and other parts as well Examples thereof include a method of printing or coating, and then drying the printing or coating film.

Further, as a method for forming a printed layer in the present invention, printing ink is printed or coated only on the content visually recognizing part of one layer constituting the packaging material of the present invention to form a printed layer constituting the content visually recognizing part. Similarly, printing ink is printed or coated only on the other part of the layer different from the above layer to form a printing layer constituting the other part, and the two printing layers are bonded to each other. There is a method of forming the entire printed layer by providing the printed layer constituting the content visually recognizing part and the layer constituting the other part in separate layers and bonding them together by a method described later. Specifically, for example, the base material layer is provided with a printing layer that constitutes a content viewing portion by printing or coating the printing ink, and the intermediate layer is further provided with a printing layer that constitutes another portion. The printing layer of the whole packaging material can be formed by providing printing ink by printing or coating, and bonding together through an adhesive layer so that both printing layers may oppose. Similarly, for example, the intermediate layer is provided with a print layer that constitutes the content viewing portion, and the second intermediate layer is provided with a print layer that constitutes the other portion, so that the print layers face each other, By bonding together via an adhesive layer, a printed layer of the entire packaging material can be formed. Since the printing ink contains pigments, the printing layer is poor in flexibility, and if the printing layer is provided in only one layer (base material layer, intermediate layer, heat sealable resin layer), the printing layer and the printing layer are separated. Peeling may occur between the provided layers. Therefore, the printing layer is provided by forming the printing layer constituting the contents visually recognizing part and the printing layer constituting the other part in separate layers and bonding them through an adhesive layer having a stress relaxation action. As a result, it is possible to prevent peeling between the printed layer and the layer provided with the printed layer.
Note the thickness of the printed ^{layer, 0.5g / m 2 ~20g / m} 2, ^{preferably, 1.0g / m 2 ~10g / m} 2 is desirable.

  Further, as described above, in the present invention, the printing layer can be composed of two or more layers, but as a method for forming a printing layer comprising two or more layers, overprint printing, double coating or the like can be mentioned.

(3) Heat-sealable resin layer In the present invention, as the heat-sealable resin constituting the heat-sealable resin layer, resins that can be melted by heat and fused to each other can be used. , Low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-acrylic acid copolymer, ethylene-ethyl acrylate copolymer, ethylene -Methacrylic acid copolymer, ethylene-methyl methacrylate copolymer, ethylene-propylene copolymer, methylpentene polymer, polybutene polymer, polyolefin resin such as polyethylene or polypropylene, acrylic acid, methacrylic acid, maleic acid, fumaric acid , Unsaturated carbohydrate such as maleic anhydride Acid-modified polyolefin resin modified with acid, polyvinyl acetate resin, poly (meth) acrylic resin, polyvinyl chloride resin, polystyrene resin, polyacrylonitrile resin, acrylonitrile-styrene copolymer (AS system) Resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), and the like. In the present invention, the heat-sealable resin layer can be composed of a resin film or sheet as described above, or a coating film made of a resin composition mainly composed of the resin as described above. The thickness is 1 to 200 μm, preferably 5 to 100 μm.

  Furthermore, in the present invention, an ethylene-α / olefin copolymer polymerized using a metallocene catalyst can also be used as the heat-sealable resin as described above. Specifically, an ethylene-α / olefin copolymer polymerized by using a metallocene catalyst, for example, a catalyst by a combination of a metallocene complex and an alumoxane, such as a catalyst by a combination of zirconocene dichloride and methylalumoxane, ie, a metallocene catalyst It is possible to use an ethylene-α / olefin copolymer obtained by polymerization using The metallocene catalyst is also called a single site catalyst because the current catalyst is called a multi-site catalyst with heterogeneous active sites, while the active sites are uniform. For example, trade name “Kernel” manufactured by Mitsubishi Chemical Corporation, trade name “Evolue” manufactured by Mitsui Petrochemical Co., Ltd., trade name “EXACT” manufactured by EXXON CHEMICAL, USA, US An ethylene-α / olefin copolymer polymerized using a metallocene catalyst such as “Affinity” or “Engage” manufactured by Dow Chemical Co. can be used. . In the present invention, when an ethylene-α / olefin copolymer polymerized using a metallocene catalyst is used as the heat-sealable resin as described above, low-temperature heat sealing is possible when manufacturing a bag. Has the advantage of being.

  In the present invention, a heat-sealable resin layer can be provided on the outermost layer of the laminated material as shown in FIG. 4. As the heat-sealable resin used for such an outermost layer, the heat seal mentioned above is used. The resin, its film or sheet can be used as it is. The thickness of the film or sheet is 5 μm to 300 μm, preferably 10 μm to 100 μm. In the present invention, the heat sealable resin layer as described above is also provided on the outermost layer, the innermost layer surface and the outermost layer surface are overlapped, and the end portion of the polymerization surface is heat sealed to form a seal portion. By doing so, the packaging container of the present invention can be manufactured.

(5) Others Usually, when packaging various items, packaging containers are often placed under harsh conditions both chemically and physically. In order to cope with such conditions, In the present invention, in addition to the above materials, a resin film or sheet constituting a normal soft packaging bag can be used as appropriate. Specifically, low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-ethyl acrylate copolymer 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, poly ( (Meth) acrylic resin, polyacrylonitrile resin, polystyrene resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), polyester resin, polyamide resin, Polycarbonate A resin, a polyvinyl alcohol resin, a saponified ethylene-vinyl acetate copolymer, a fluorine resin, a diene resin, a polyacetal resin, a polyurethane resin, a film or a sheet of a known resin such as nitrocellulose is arbitrarily selected. Can be used. In addition, for example, a film such as cellophane, a synthetic paper, or the like can be used. In the present invention, the resin film or sheet may be any of unstretched, uniaxially or biaxially stretched. Moreover, although the thickness is arbitrary, it can select and use from the range of several micrometers-300 micrometers. Further, in the present invention, the resin film or sheet may be a film having any property such as extrusion film formation, inflation film formation, and coating film.

3. Method for Producing the Packaging Material of the Present Invention In the present invention described above, a method for producing the packaging material of the present invention using the material as described above will be described. In order to produce the packaging material of the present invention, first, as described above, a gas barrier layer or a printed layer is formed on the base layer, intermediate layer, heat sealable resin layer, etc., and then the gas barrier is formed. The base layer, intermediate layer, heat-sealable resin layer, etc. provided with the adhesive layer or the print layer are bonded together. As a method of laminating the base material layer, the intermediate layer, the heat-sealable resin layer, etc., a lamination method used when producing a normal packaging material, for example, a wet lamination method, a dry lamination method, a solventless dry lamination , Extrusion lamination method, T-die coextrusion molding method, coextrusion lamination method, inflation method and the like. In the present invention, when performing the above-mentioned lamination, if necessary, pretreatment such as corona treatment and ozone treatment can be applied to the film. For example, isocyanate (urethane), polyethyleneimine Anchor coating agents such as polyurethane, polybutadiene, organic titanium, or other anchor coating agents such as polyurethane, polyacrylic, polyester, epoxy, polyvinyl acetate, cellulose, etc. An agent or the like can be used.

  In the manufacturing method of the packaging material as described above, examples of the extrusion resin constituting the adhesive layer in extrusion lamination include polyethylene, ethylene-α-olefin copolymer, polypropylene, polybutene, polyisobutene, poisobutylene, and polybutadiene. , Copolymers of ethylene and unsaturated carboxylic acids such as polyisoprene, ethylene-methacrylic acid copolymers, or ethylene-acrylic acid copolymers, or acid-modified polyolefin resins obtained by modifying them, ethylene-ethyl acrylate Copolymers, ionomer resins, ethylene-vinyl acetate copolymers and the like can be used. In the present invention, the adhesive constituting the adhesive layer when dry laminating is specifically a two-component curable urethane adhesive, polyester urethane adhesive, Ether urethane adhesives, acrylic adhesives, polyester adhesives, polyamide adhesives, polyvinyl acetate adhesives, epoxy adhesives, rubber adhesives, and the like can be used.

4). Next, a method for producing a packaging container using the packaging material of the present invention will be described. There are various methods as this method. The packaging material of the present invention can be produced by using the packaging material of the present invention, superimposing the heat-sealable resin layer surfaces facing each other, and further heat-sealing the peripheral edge portion to provide a seal portion. In the above, the form of heat-sealing the peripheral edge is, for example, a side seal type, a two-side seal type, a three-side seal type, a four-side seal type, an envelope-attached seal type, a palm-attached seal type (pillow seal type), and a pleat Heat seal forms such as a seal type, a flat bottom seal type, a square bottom seal type, a ship bottom seal type, and the like can be given, and various types of packaging containers suitable for this can be manufactured. In addition, for example, a self-supporting packaging bag (standing pouch) or the like can be manufactured. In the above, as a heat sealing method, for example, a known method such as a bar seal, a rotary roll seal, a belt seal, an impulse seal, a high frequency seal, and an ultrasonic seal can be used.

5. Use of packaging container of the present invention In the present invention, the packaging container of the present invention produced as described above can be used for filling and packaging various articles, for example, filling and packaging articles such as medicines and food and drinks. It is suitable for doing. In particular, when the packaging container of the present invention is used for filling and packaging liquids such as nutrients or semi-solid medicines and foods and drinks, the contents are in a specific wavelength region of ultraviolet to visible short wavelength region. It is possible to prevent the quality and the like of the contents from being deteriorated due to the influence of the light beam, and to prevent the quality of the contents from deteriorating, and it is possible to accurately adjust the dose and the administration rate. Further, in the present invention, a packaged product formed by filling and packaging the above articles can be easily inspected for the presence or absence of foreign substances such as metal using a metal detector or the like.

Next, the present invention will be specifically described with reference to examples.
Example 1
(1) A biaxially stretched polyethylene terephthalate film having a thickness of 12 μm is used as the base material layer, and the contents visually recognizing part and other parts are formed on this one side by the gravure printing method in the order shown in the following (Table 1). Printing ink was continuously printed to form a printing layer.

(2) On the other hand, a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was used as an intermediate layer, and an aluminum oxide vapor deposition film and a gas barrier coating film were sequentially laminated as a gas barrier layer on one side by the following method. did. That is, a 200-aluminum aluminum oxide vapor deposition film was laminated on one surface of the intermediate layer by physical vapor deposition, and a composition prepared according to the composition shown in the following (Table 2) on the vapor deposition film: a. And composition b. A colorless transparent barrier coating solution consisting of a mixed solution with the above is coated by a gravure roll coating method, heated at 100 ° C. for 30 seconds, and a gas barrier coating film of 0.4 g / m ^{2 in} a dry operation state is formed. Formed.

(3) Next, a two-component curable urethane-based adhesive is used as an adhesive layer on the printed layer surface of the substrate layer on which the above-described printed layer is laminated, and a thickness of 3.5 g / m ^{2 in} a dry state by a gravure coating method. It was provided so as to face the intermediate layer surface of the intermediate layer on which the gas barrier layer was laminated, and was bonded by a gravure coating method. Furthermore, a two-component curable urethane-based adhesive is provided as an adhesive layer on the gas barrier layer surface so as to have a thickness of 3.5 g / m ^{2 in} a dry state by a gravure coating method, and is a second intermediate layer. It was bonded to a 15 μm biaxially stretched nylon film by a gravure coating method. Next, a two-component curable urethane-based adhesive is provided on the opposite surface of the second intermediate layer as an adhesive layer so as to be 3.5 g / m ^{2 in a} dry state by a gravure coating method, and as a heat-sealable resin layer A 70 μm unstretched polypropylene film was used, and this was opposed to the adhesive layer by a gravure coating method to produce a packaging material according to the present invention consisting of a content visually recognizing portion and other portions.

Example 2
A biaxially stretched nylon film having a thickness of 15 μm is used as the second intermediate layer, and a vapor barrier film having a thickness of 100 で by chemical vapor deposition is formed on one side of the second intermediate layer as a gas barrier layer. A gas barrier in which a gas barrier coating film is sequentially laminated by the same method as shown in (2) above, and the second intermediate layer surface of the second intermediate layer on which the gas barrier layer is laminated is provided on the intermediate layer. Example 1 except that the adhesive layer surface and the adhesive layer are bonded together, and the gas barrier coating surface provided on the second intermediate layer is bonded via the heat-sealable resin layer and the adhesive layer. By this method, the packaging material of the present invention consisting of the contents visually recognizing part and other parts was produced.

Example 3
Other than laminating a vapor barrier film of 100 liters of organic silicon oxide by chemical vapor deposition and a gas barrier coating film by the same method as shown in (2) of Example 1 as a gas barrier layer on one side of the intermediate layer Manufactured the packaging material of this invention which consists of a content visual recognition part and another part by the method similar to Example 2. FIG.

Example 4
The same method as in Example 1 except that the printing inks constituting the content visualizing portions 1 and 2 were continuously printed by the gravure printing method in the order shown in Table 3 below to form a printing layer. Thus, the packaging material of the present invention consisting of only the contents visually recognizing part was formed.

Comparative Example 1
A biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was used as the base material layer, and a gas barrier layer was formed on this surface as a gas barrier layer with a vapor deposition film of 200 mm of aluminum oxide by physical vapor deposition, as shown in Example 2 (2). A gas barrier coating film was sequentially laminated in the same manner as described above. Next, each printing ink was continuously printed on the gas barrier layer by the gravure printing method in the same order as in Example 1 to form the printed layer.
After the printing layer is formed, a two-component curable urethane adhesive is provided thereon as an adhesive layer so as to have a thickness of 3.5 g / m ^{2 in} a dry state by a gravure coating method, and an intermediate layer having a thickness of 15 μm. A biaxially stretched nylon film was used, and this was opposed to the print layer, and bonded by a gravure coating method. Further, a two-component curable urethane adhesive is provided on the back surface of the intermediate layer as an adhesive layer so as to have a thickness of 3.5 g / m ^{2 in} a dry state by a gravure coating method. A stretched polypropylene film was used, and this was opposed to the adhesive layer by a gravure coating method to produce a packaging material.

Comparative Example 2
Example 1 except that each printing ink was continuously printed in the order shown in the following (Table 4) by the gravure printing method and the printing ink was continuously printed on the portion corresponding to the content viewing portion and the other portion. A packaging material was produced in the same manner as described above.

Comparative Example 3
Example 1 except that each printing ink was continuously printed in the order shown in the following (Table 5) by the gravure printing method and the printing ink was continuously printed on the part corresponding to the content visually recognizing part and the other part. A packaging material was produced in the same manner as described above.

Comparative Example 4
Example 1 except that each printing ink was continuously printed in the order shown in the following (Table 6) by the gravure printing method and the printing ink was continuously printed on portions corresponding to the content viewing portion and other portions. A packaging material was produced in the same manner as described above.

Comparative Example 5
A packaging material was produced in the same manner as in Example 1 except that the gas barrier layer was not laminated on the intermediate layer.

1. Evaluation of oxygen permeability and water vapor permeability after retorting of packaging materials of Examples 1 to 4 and Comparative Examples 1 to 5 Using the packaging materials of Examples 1 to 4 and Comparative Examples 1 to 5, the bag making machine A flat pouch having a size of 125 mm × 150 mm (of which the content visible portion is 10 mm × 100 mm) was prepared. The appearance of the flat pouch was as shown in FIG. The flat pouch thus prepared was filled with tap water as the contents, and steam retort sterilization was performed at 121 ° C. for 30 minutes and 2.1 atm.
Next, before and after the retort sterilization treatment, the oxygen permeability of the packaging materials of each of the above examples and comparative examples was measured under the measurement conditions of 23 ° C./90 RH% (JIS standard K7126) using OX-TRAN 2/20 manufactured by MOCON. The water vapor permeability was measured with PERMATRAN manufactured by MOCON under the measurement conditions of 40 ° C./90 RH% (JIS standard K7129). The results are shown below (Table 7).

"Evaluation results"
As described above, the packaging materials of Examples 1 to 4 in which the gas barrier layer was laminated on the intermediate layer or the second intermediate layer were compared with Comparative Example 5 in which the gas barrier layer was not laminated, before and after the retort treatment. Has been confirmed to be significantly superior.
For example, when the oxygen permeability and water vapor permeability before retorting of Example 1 are compared with Comparative Example 5, the oxygen permeability and water vapor permeability of Example 1 are 0.3, respectively. In Example 3,> 60 and 6.5, respectively, and Example 1 is superior to Comparative Example 3 in terms of oxygen permeability and water vapor permeability of about 200 times or more and about 21.3 times, respectively. It was confirmed. Similarly, when Example 1 after retorting is compared with Comparative Example 3, Example 1 is superior to Comparative Example 3 in terms of oxygen permeability and water vapor permeability of about 200 times or more and about 3.6 times, respectively. It was confirmed to be a thing.

2. Appearance evaluation after retort treatment 125 mm × 150 mm using the packaging materials of Examples 1 to 4 and Comparative Examples 1 to 5 (of which the contents visible portion is 10 mm × 100 mm). ) Flat pouch. These flat pouches were filled with tap water, and steam retort sterilization was performed at 121 ° C. for 30 minutes and 2.1 atm. After one month of steam retort sterilization, the presence or absence of delamination (delamination) between the base material layer, the intermediate layer, or the second intermediate layer, and the inorganic oxide deposited film constituting the gas barrier layer was visually confirmed. The results are shown below (Table 8).

"Evaluation results"
As described above, the packaging material of Examples 1 to 4 provided so that the printed layer does not contact the gas barrier layer is compared with the packaging material of Comparative Example 1 provided so that the printed layer contacts the gas barrier layer. Adhesion between the biaxially stretched polyethylene terephthalate film or biaxially stretched nylon film constituting the base material layer or the intermediate layer and the inorganic oxide vapor deposited film constituting the gas barrier layer, that is, resistance to steam retort sterilization It was confirmed that the moisture resistance was improved.
For example, the packaging material of Example 1 is obtained by laminating a printing layer on a base material layer, laminating a gas barrier layer on an intermediate layer, and further bonding the printing layer surface and the intermediate layer surface so as to face each other, that is, the printing layer. Are provided so as not to come into contact with the gas barrier layer, but even after one month after the steam retort sterilization treatment, no delamination is observed between the layers, and the biaxially stretched polyethylene terephthalate film or biaxial film constituting the intermediate layer It was confirmed that the adhesion between the stretched nylon film and the inorganic oxide deposited film constituting the gas barrier layer was good.
On the other hand, the packaging material of Comparative Example 1 is provided with a gas barrier layer provided on a base material layer and a print layer provided on the gas barrier layer, that is, a print layer provided in contact with the gas barrier layer. In this packaging material, one month after the steam retort sterilization treatment, peeling was observed between the biaxially stretched polyethylene terephthalate film constituting the base material layer and the inorganic oxide vapor deposition film constituting the gas barrier layer. It was confirmed that the adhesion between the deposited inorganic oxide film was inferior.

3. Sensory evaluation 125 mm × 150 mm using the packaging materials of Examples 1 to 4 and Comparative Examples 1 to 5 (of which the contents visible portion is 10 mm × 100 mm). ) Flat pouch. These flat pouches are filled with commercially available natural water, and steam retort sterilization is performed at 121 ° C. for 30 minutes and 2.1 atm. The taste of the natural water after steam retort sterilization is three levels (5 persons) ○: delicious, Δ: slightly bitter, ×: bad) The results are shown below (Table 9).

実施例１〜４の包装材料は、ガスバリア性層と接しないように印刷層を設けたものであるが、これらを用いて製造した包装容器に天然水を充填し、蒸気レトルト殺菌処理を行っても、天然水の味に変化はなく、蒸気レトルト殺菌処理耐性等の防湿性に優れることが確認された。これに対し、ガスバリア性層を有さない比較例５の包装材料を用いて製造した包装容器においては、蒸気レトルト殺菌処理後、天然水の味が変質し、防湿性に劣ることが確認された。またガスバリア性層と接するように印刷層を設けた比較例１の包装容器を用いて製造した包装容器においても、天然水の味がやや変質し、防湿性に劣ることが確認された。

The packaging materials of Examples 1 to 4 are provided with a printing layer so as not to come into contact with the gas barrier layer, but are filled with natural water in a packaging container manufactured using these and subjected to steam retort sterilization treatment. However, it was confirmed that there was no change in the taste of natural water and it was excellent in moisture resistance such as steam retort sterilization resistance. On the other hand, in the packaging container manufactured using the packaging material of Comparative Example 5 that does not have a gas barrier layer, it was confirmed that the taste of natural water changed after steam retort sterilization and was inferior in moisture resistance. . Moreover, also in the packaging container manufactured using the packaging container of the comparative example 1 which provided the printing layer so that a gas barrier layer might be contact | connected, the taste of natural water changed a little and it was confirmed that it is inferior to moisture resistance.

  That is, it was confirmed that moisture resistance such as steam retort sterilization resistance was improved by providing a gas barrier layer on any layer of the packaging container and providing a printing layer so as not to contact the gas barrier layer.

4). Evaluation of light shielding properties About the packaging materials of Examples 1 to 4 and Comparative Examples 1 to 5, the content visually recognizing part (the content visually recognizing part 1 in Example 4) and the other part (in Example 4 the content visually recognizing) The light transmittance of part 2) from 250 nm to 800 nm was measured with a Shimadzu ultraviolet visible absorption spectrometer (UV-2400). FIG. 10A shows the results of evaluating the light shielding properties at the contents visually recognizing portion, and FIG.

"Evaluation results"
The content visual recognition part of Examples 1-3 and the content visual recognition part 1 of Example 4 formed the printing layer with the scarlet ink or the yellow ink, and the content visual recognition part 2 of Example 4 is white. Although the printing layer is formed with ink and amber ink, both show low transmittance of 20% or less for light in the wavelength region of 250 nm to 550 nm, and for light in the wavelength region of 650 nm to 800 nm. The transmittance was as high as 80% or more.

  On the other hand, the content visualizing part of Comparative Example 2 and Comparative Example 3 in which the printing layer was not formed, and the other part of Comparative Example 3 in which the printing layer was formed only with the white ink were from 250 nm to about 300 nm. Although it shows light-shielding properties for light in the wavelength region, the light transmittance rapidly increases around 300 nm, and the transmittance from 350 nm to 800 nm is very high at about 90% or more, and the wavelength region from 250 nm to 550 nm. The light beam could not be effectively shielded. On the other hand, the content visually recognizing part of Comparative Example 4 in which a printing layer was formed with a white ink containing a white pigment and a gray ink containing a white pigment and a black pigment was about 10% or less over the entire wavelength region of 250 nm to 800 nm. A low light transmittance was exhibited.

  In other words, by using printing ink containing a specific pigment such as amber pigment, amber pigment called yellow ink, a yellow pigment, or a combination of a yellow pigment and a red pigment as a material for forming a printing layer, protein or carbohydrate It was confirmed that only light in a specific wavelength region of 250 nm to 550 nm involved in modification / decomposition such as can be shielded with a low light transmittance of 20% or less.

5. Contents visibility and print appearance evaluation 125 mm × 150 mm using the packaging materials of Examples 1 to 4 and Comparative Examples 1 to 5 (of which the contents visible portion is 10 mm × 100 mm). ) Flat pouch. These flat pouches are filled with a specified amount of commercially available nutritional food (protein and sugar-containing) powder dissolved in water, and the contents are visible in the visible portion of the flat pouch, and the appearance of other parts is visually observed. It was evaluated with. The results are shown below (Table 10).

"Evaluation results"
(1) Evaluation result of content visibility The content visual recognition part of the flat pouch of Examples 1 to 4 exhibits a low transmittance of 20% or less with respect to light rays in the wavelength region of 250 nm to 550 nm, and 650 nm to 800 nm. Comparative example 2 and comparative example in which the content visibility in these flat pouches does not have light-shielding properties, although it shows a high transmittance of 80% or more with respect to the light in the wavelength region of Compared with 3 flat pouches, it is possible to confirm the contents of both, and the flat pouches of Examples 1 to 4 are those of Comparative Example 2 and Comparative Example 3 in which the content visually recognizing part does not have light-shielding properties. Excellent contents visibility equivalent to a flat pouch. On the other hand, in the flat pouch of Comparative Example 4 in which the content visually recognizing portion has low light transmittance over the entire wavelength region of 250 nm to 800 nm, the remaining amount of the content cannot be confirmed, and the content visually recognized It was inferior in nature.
That is, by using a packaging material having a certain transmittance or more for light in the wavelength region of 650 nm to 800 nm as the content viewing portion, excellent content visibility equivalent to that of a packaging container having no light shielding properties is obtained. It was confirmed that

(2) Evaluation Results of Print Appearance The other parts of Examples 1 to 3 were formed by continuously printing white ink and gray ink to form a printed layer of other parts, and the contents of Example 4 The visible portion 2 was formed by continuously printing the white ink and the amber ink, and other portions were formed, and a good printed image that did not hinder the printing of the product name or the pattern was obtained.

6). Evaluation of storage stability 125mm x 150mm flat pouch using the packaging materials of Examples 1 to 4 and Comparative Examples 1 to 5 (of which the contents are visible) 10 mm × 100 mm). These flat pouches are filled with a specified amount of commercially available nutritional food (containing protein and carbohydrates) dissolved in water, and after retorting, stored for 1 month under fluorescent light at 23 ° C and 40% RH. Then, the contents were evaluated for discoloration. The results are shown below (Table 11).

"Evaluation results"
The flat pouches of Examples 1 to 3 have a high gas barrier property, and the contents visually recognizing portion has a low transmittance of 20% or less with respect to a light beam having a wavelength region of 250 nm to 550 nm, and a wavelength region of 650 nm to 800 nm. The other portion has a high transmittance of 80% or more with respect to the light beam of the other, and the other portion has a low transmittance of 20% or less with respect to the light rays in all wavelength regions. The flat pouch of Example 4 has a high gas barrier property, has a low transmittance of 20% or less for light in the wavelength region of 250 nm to 550 nm, and 80% for light in the wavelength region of 650 nm to 800 nm. It consists only of the content visualizing part which has the above high transmittance | permeability.

  That is, all of the flat pouches of Examples 1 to 4 have high gas barrier properties and high light blocking properties with respect to light in the wavelength region of 250 nm to 550 nm. When compared with the flat pouch of Comparative Example 4 having high gas barrier properties and high light shielding properties for light in all wavelength regions, no discoloration of the contents was observed in the evaluation after one month. It was confirmed that this flat pouch has excellent storage stability equivalent to the flat pouch of Comparative Example 4.

  On the other hand, in Comparative Example 2 in which the content visually recognizing part does not have light shielding properties, and in the flat pouch in Comparative Example 3 in which both the content visually recognizing part and other parts do not have light shielding properties, one month later In the evaluation, the contents changed color, and it was confirmed that the storage stability was inferior to that of the flat pouches of Examples 1 to 4. Similarly, in the flat pouch of Comparative Example 5 inferior in gas barrier properties, it was confirmed that the contents were discolored in the evaluation after one month and inferior in storage stability.

  That is, as a packaging material, by using a material having both high gas barrier properties and high light shielding properties for light in the wavelength region of 250 nm to 550 nm, it is equivalent to a packaging container having light shielding properties for light in all wavelength regions. It was confirmed that storage stability was obtained.

7). Summary of Evaluation Results As described above, by producing a packaging material so that the printed layer and the gas barrier layer do not contact with each other, a biaxially stretched polyethylene terephthalate film or a biaxially stretched nylon film constituting a base material layer, an intermediate layer, etc. It was confirmed that the adhesion between the vapor-deposited inorganic oxide film constituting the gas barrier layer, that is, moisture resistance such as steam retort sterilization treatment resistance was improved.
Furthermore, a gas barrier layer is laminated on a base material layer, an intermediate layer, etc. constituting the packaging material to give a high gas barrier property, and a part or all of it shields only light in a specific wavelength region of 250 nm to 550 nm. It was confirmed that a packaging container having both excellent storability and contents visibility was obtained by shielding the light in all wavelength regions from the rest.

It is a schematic plan view which shows an example of the external appearance of the packaging material of this invention. It is a schematic sectional drawing which shows an example of the laminated constitution of the packaging material of this invention. It is a schematic sectional drawing which shows an example of the laminated constitution of the packaging material of this invention. It is a schematic sectional drawing which shows an example of the laminated constitution of the packaging material of this invention. It is a schematic sectional drawing which shows an example of the laminated constitution of the packaging material of this invention. It is a schematic sectional drawing which shows an example of the laminated constitution of the packaging material of this invention. It is a schematic perspective view which shows the structure of the packaging container of this invention formed into a bag using the packaging material shown in FIG. It is a schematic perspective view which shows the structure of the packaged product which filled and packaged the contents in the packaging container shown in FIG. It is a schematic plan view which shows the external appearance of the packaging container formed into a bag using the packaging material of Examples 1-4 or Comparative Examples 1-5. It is a figure which shows the measurement result of the light transmittance of 250 nm-800 nm of the contents visual recognition part of the packaging container of Examples 1-4 and Comparative Examples 1-5. It is a figure which shows the measurement result of the light transmittance of 250 nm-800 nm of the other part of the packaging container of Examples 1-4 and Comparative Examples 1-5.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Contents visual recognition part 2 Other parts 3 Base material layer 4, 4a Heat-sealable resin layer 5 Intermediate layer 5a Second intermediate layer 6, 6a Gas barrier layer 7 Print layer which constitutes content visual recognition part 8 Other parts 9 Heat-seal part 10 Contents 11 Top seal part 12 Notch for opening A Packaging material B Packaging material C Packaging material D Packaging material E Packaging material F Packaging material G Packaging container H Packaging product

Claims (13)

In a packaging material made of a laminate having at least a base material layer made of a resin film, an intermediate layer made of a resin film, a printed layer, and a heat-sealable resin layer,
A gas barrier layer is provided on one or both surfaces of the base material layer and the intermediate layer,
The printed layer is provided so as not to contact the gas barrier layer, and further, part or all of the packaging material is 20% or less in a wavelength region of 250 nm to 550 nm, and the transmittance further shifts to a longer wavelength region. A packaging material characterized in that it is a content-viewing part that rises and has a light transmittance of 50% or more in the wavelength region of 650 nm to 800 nm, and the other part has a total light transmittance of 20% or less.   The packaging material according to claim 1, wherein the content visually recognizing portion has a light transmittance of 10% or less in a wavelength region of 250 nm to 550 nm.   The pigment used for the printed layer of the contents visually recognizing part is one or more selected from the group consisting of amber pigments, yellow pigments, and a mixture of amber pigments or yellow pigments and red pigments The packaging material according to claim 1, wherein the packaging material is the above pigment.   One side of the printing layer is in contact with either the base material layer, the intermediate layer, or the heat-sealable resin layer, and the other side is another base material layer, the intermediate layer, or the heat-sealable resin layer. The packaging material according to any one of claims 1 to 3, wherein the packaging material is provided so as to be in contact with any one of the layers through an adhesive layer.   The packaging material according to any one of claims 1 to 4, wherein a printing layer is provided on the base material layer.   The packaging material according to claim 1, further comprising a second intermediate layer made of a resin film.   The packaging material according to claim 5, wherein the second intermediate layer has puncture resistance.   The packaging material according to claim 5 or 6, wherein a gas barrier layer is provided on one surface of the second intermediate layer, and a printed layer is provided so as not to contact the gas barrier layer.   The packaging material according to any one of claims 1 to 4, wherein the gas barrier layer is a vapor-deposited film of an inorganic oxide. The gas barrier layer comprises an inorganic oxide vapor-deposited film and a general formula R ¹ _n M (OR ² ) _m (wherein M represents a metal atom, and R ¹ and R ² represent an organic group having 1 to 8 carbon atoms. N is an integer of 0 or more, m is an integer of 1 or more, and n + m represents a valence of M), and at least one alkoxide, polyvinyl alcohol, and / or ethylene vinyl alcohol The alkoxide hydrolyzate obtained by polycondensation by a sol-gel method or a gas barrier coating film which is an alkoxide hydrolyzate condensate. The packaging material according to any one of the above.   The packaging material according to claim 9 or 10, wherein the inorganic oxide is aluminum oxide or silicon oxide.   The packaging material according to claim 9 or 10, wherein the resin film having an inorganic oxide vapor deposition film is formed by laminating organic silicon oxide on the resin film by a chemical vapor deposition method.   It is a packaging container for nutrients using the packaging material as described in any one of Claims 1-12, Comprising: The heat-sealable resin layer side of one packaging material, and the heat-sealable resin of the other packaging material A packaging container, wherein the layer side is overlapped so as to face each other, and the end thereof is heat sealed.

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