JP2003146322A - Paper cup - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a paper cup in which a crack or the like is prevented from being generated at a vapor deposited film of non-organic oxide such as silicon oxide, aluminum oxide or the like constituting a transparent barrier film acting as a barrier raw material, occurrence of pin-holes or the like is completely eliminated, a superior barrier property for preventing oxygen gas and water vapor of the like from being passed through the paper cup is attained, a defective sealing and a liquid leakage or the like are prohibited when the pin-holes are generated, deterioration of the stored contents is prohibited, and it has a superior keeping property and storing property. SOLUTION: There is provided a paper cup composed of a cylindrical cup- barrel member and a bottom member for use in sealingly closing the bottom part of the cylindrical cup barrel member. This is a paper cup in which the cylindrical cup barrel member and the bottom member are constituted by a laminated member having at least the outermost layer; paper base material; an adhesive agent layer composed of two layers of polyolefin resin layer; a barrier-like layer constituted by a vapor deposited film of non-organic oxide and a gas barrier-coated film at one surface of the base material film; and the inner-most layer stacked in sequence.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a paper cup,
More specifically, it has an excellent barrier property to prevent the permeation of oxygen gas, water vapor, etc. Furthermore, it prevents pinholes from occurring, prevents seal failure, liquid leakage, etc., and prevents alteration of the contents, etc. The present invention also relates to a paper cup that is excellent in storability and storability.

[0002]

2. Description of the Related Art Conventionally, paper cups of various forms have been used for filling and packaging various liquid foods and drinks such as alcoholic beverages, fruit juices, soft drinks, dairy beverages, liquid seasonings, etc.
Developed and proposed. In recent years, as a barrier material, vapor deposition of an inorganic oxide such as silicon oxide or aluminum oxide on one surface of a base film such as a biaxially stretched polyethylene terephthalate film or a biaxially stretched nylon film. A transparent barrier film provided with a film attracts attention, and a paper cup using this as a barrier material is
Developed and proposed. That is, as shown in FIG. 11, first, at least the polyolefin resin layer 61 is formed.
(Heat sealable resin layer) / paper base material 62 / adhesive resin layer 63 / base material film 6 provided with a vapor deposition film 64 of inorganic oxide
5 / Polyolefin resin layer 66 (heat-sealable resin layer) is laminated in this order to produce a laminated material 67, which is then used to form the body of a paper cup. The blank plate 68 is punched into a predetermined shape to form a blank plate 68, and then the blank plate 68 is rolled into a tubular shape, and both end portions thereof are partially overlapped with each other, and the overlapped portion is frame-treated, or Performs heat treatment such as hot air treatment,
The polyolefin resin layer (heat-sealable resin layer) present in the above-mentioned polymerized portion is heated and melted, and then pressed by a hot plate or the like to be stuck on the body to form the body-sealed portion 69. The tubular cup body 70 that constitutes the paper cup is manufactured. On the other hand, the laminated material 67 that constitutes the blank plate 68 described above.
Using the same laminated material 67 as described above, a circular plate 71 is punched to manufacture a disk 71 that constitutes the bottom part, and then the outer peripheral portion of the disk 71 is erected into a cylindrical shape, and the erected forming part is formed. 72
To produce a bottom 73 having Then, the cylindrical cup body 70 manufactured as described above is attached to the bottom part 7 manufactured as described above.
3 and then the cylindrical cup body 70 and the bottom 73 are blown to the joints thereof with hot air or the like so that a polyolefin resin layer (heat-seal resin layer) existing at the joints ) 61 and 66 are melted by heating, and then the tip portion 74 of the tubular cup body 70 is bent inward by a curling die, and is covered on the upright forming portion 72 constituting the bottom portion 73 ( (Refer to arrow P ₃ ), the above-mentioned cylindrical cup body 7
The overlapping portion of the front end portion 74 of No. 0 and the upright molding portion 72 of the bottom portion 73 is knurled from the inner diameter side by a knurling, whereby the tubular cup body portion 70 and the bottom portion 73 are closely adhered. To form the joint portion 75, and thereafter, the tip end portion of the tubular cup body portion 70 on the side opposite to the side to which the bottom portion 73 is attached is outwardly moved by a curling die as described above. The paper cup K is manufactured by curling while bending (see P ₄ ) to form the upper end flange portion 76. Then, although not shown, the paper cup manufactured as described above is delivered to a maker or the like for filling the contents, and then the paper cup is supplied to a contents filling machine. The contents are filled from the opening, and then the lid material or the like is tightly adhered to the upper end flange portion of the paper cup to seal the opening, thereby manufacturing the paper cup packaging body in which the contents are filled and packaged. . In addition, although not shown, normally, penetration of contents,
In order to prevent liquid leakage and the like, the inner end surface of the seal portion constituting the tubular cup body portion is subjected to end surface treatment by, for example, skiving / hemming treatment or the like.

[0003]

However, in the above paper cup, the biaxially stretched polyethylene terephthalate film or the biaxially stretched polyethylene terephthalate film is used as the barrier material.
When a transparent barrier film having a vapor-deposited film of an inorganic oxide such as silicon oxide or aluminum oxide provided on one surface of a base film such as an axially stretched nylon film is used, the silicon oxide forming the transparent barrier film is used. Since a vapor deposition film of an inorganic oxide such as aluminum oxide is a glassy, inflexible thin film and is a film lacking remarkably flexibility, for example, from outside, heat or pressure may be applied. There is a problem that cracks etc. easily occur due to the action,
Thus, once a crack or the like occurs in a vapor deposition film of an inorganic oxide such as silicon oxide or aluminum oxide, the barrier property for preventing the permeation of oxygen gas, water vapor, etc. is remarkably lacking, and it is no longer usable. There are drawbacks. For example, a paper substrate and the above-mentioned transparent barrier film are treated with silicon oxide,
A low density polyethylene resin or the like is used, with the surfaces of the vapor deposition films of an inorganic oxide such as aluminum oxide facing each other, through an anchor coating agent layer or the like, and this is heated to about 330 ° C. and extruded. When melt-extruded from a machine or the like and laminated through the melt-extruded resin layer, cracks or the like easily occur in the vapor deposition film of inorganic oxide such as silicon oxide or aluminum oxide due to the heating temperature by the melt-extruded resin layer. , Oxygen gas,
The barrier property of preventing permeation of water vapor etc. is significantly deteriorated.

As a member constituting the above paper cup, at least a polyolefin resin layer (heat
Tosile resin layer) / paper substrate / adhesive resin layer / substrate film provided with a vapor deposition film of inorganic oxide / polyolefin resin layer (heat-sealable resin layer) When a material is used, a low-density polyethylene resin is usually used as the polyolefin resin layer (heat-seal resin layer) forming the inner surface layer to form a heat-seal resin layer. Formed, but in this case,
For example, when forming a cylindrical cup body portion or bottom portion by a heat treatment of blowing hot air or the like on the inner surface thereof, when joining the both, further forming an upper end flange portion or the like. At that time, it is usually 320 ° C to 350 ° C.
When heat-sealing is carried out at a heating temperature of about ℃, and the heat-sealing is carried out under such conditions as the heating temperature, etc., a roasting pinhole is formed on the inner surface of the laminated material constituting the paper cup. However, there is a problem that it occurs extremely easily. When the pinhole is generated as described above, there is a problem that a seal failure, a liquid leak, etc. occur, and along with this, the storage property is deteriorated along with the deterioration of the content, and the stability such as the storage property is lacking. In some cases, there is a problem that the commercial value of the product is significantly reduced and the product must be discarded.

Generally, a pinhole generated in a paper cup is a roasting pinhole that is generated when the tubular cup body and the bottom are heat-treated to make a box, and they are roasted by hot air or the like. -Le and others are known. Then, the above-mentioned roasting pinhole will be described in more detail below, including the process of its generation, etc. As described above, when the paper cup is made, first of all, the tubular cup cylinder constituting the paper cup is formed. In order to form the portion or the bottom portion, heat treatment is performed by blowing hot air from the outlet of the heating chamber onto the inner surface or the outer surface of the blank plate or the disc. By the way, the hot air blown onto the inner surface or the outer surface of the blank plate or the disc as described above melts the resin layer forming the innermost layer on the inner surface, and further, the heat by the hot air reaches the paper substrate. Then, the paper base material is heated, and when the paper base material is heated, the moisture contained in the paper base material is heated, and this becomes vapor to the inner and outer surface sides of the laminated material. The resin layer or the like laminated on the inner and outer surfaces of the paper base material is pushed up due to the attempt to escape, and a foaming phenomenon of swelling is exhibited. Furthermore, when heat from hot air is applied, the resin layer on the inner surface side laminated on the paper base material,
It is believed that the vapor pressure due to the evaporation of water becomes unbearable and the swelled resin layer is broken, resulting in broiled pinholes. For example,
A low density polyethylene resin layer, a paper base material, an adhesive polyethylene resin layer, and a vapor deposition film of an inorganic oxide were provided from the outer surface side. 2
Using an axially stretched polyethylene terephthalate film, a laminated material composed of a structure in which a low density polyethylene film and the like are sequentially laminated, and in a paper cup produced by box-making this, observing the generation process of the above-mentioned roasting pinhole Similarly to the above, first, in the initial stage, in the adhesive polyethylene resin layer forming the inner surface layer, this was swollen to cause a foaming phenomenon, and a vapor deposition film of an inorganic oxide was provided so as to be accompanied by the swollen 2 Confirm that the axially stretched polyethylene terephthalate film and further the low-density polyethylene film swell and foam, and finally that the above-mentioned swollen and foamed bubbles rupture to form a roasting pinhole. Is something that can be done. Therefore, the present invention prevents cracks and the like from occurring in the vapor-deposited film of an inorganic oxide such as silicon oxide and aluminum oxide that constitutes a transparent barrier film as a barrier material, and eliminates the occurrence of roasting pinholes and the like. As a result, it has an excellent barrier property to prevent permeation of oxygen gas, water vapor, etc., avoids seal failure, liquid leakage, etc. due to the occurrence of pinholes, prevents alteration of the contents, etc. Another object of the present invention is to provide a paper cup having excellent storability.

[0006]

As a result of various studies to solve the above-mentioned problems in the paper cup, the present inventor has
At least an outermost layer, a paper base material, an adhesive layer composed of two polyolefin resin layers, and a barrier property composed of a vapor deposition film of an inorganic oxide and a gas barrier coating film provided on one surface of the base film. A layer and an innermost layer are sequentially laminated to produce a laminated material, or an adhesive layer composed of at least a paper base material and two polyolefin resin layers except the outermost layer of the laminated material. A barrier layer having a structure in which a vapor deposition film of an inorganic oxide and a gas barrier coating film are provided on one surface of a base film, and an innermost layer is sequentially laminated to produce a laminated material, and Using the laminated material, first, a blank plate is punched into a desired shape, further, end face treatment such as skive / hemming is processed to form a blank plate, and then the blank plate is rolled into a tubular shape. Partially overlap both ends The polymerized portion is subjected to flame treatment, or heat treatment such as hot air treatment to heat and melt the innermost layer, or the outermost layer and the innermost layer existing in the polymerized portion, and then by a hot plate or the like. By pressing and sticking the body to form the body seal portion, a tubular cup body member that constitutes the paper cup is manufactured, while using the same laminated material that constitutes the blank plate described above. , This is punched into a circular shape to manufacture the disk that constitutes the bottom,
Then, the outer peripheral portion of the disc is formed by standing up in a tubular shape to produce a bottom member having a standing up forming portion, and then the tubular cup body member produced above is subjected to the same manner as the bottom member produced above. Insert, after that, the tubular cup body member and the bottom member, the innermost layer existing in the joint portion by blowing hot air or the like to the joint portion, or, the outermost layer and the innermost layer is heated and melted, Then, the tip of the tubular cup body is bent inward by a curling die, and is covered with the upright forming portion forming the bottom, and the tip and the bottom of the tubular cup body are formed. By knurling the overlapped portion with the upright forming portion of the material from the inner diameter side by knurling, the tubular cup body member and the bottom member are joined to form a joined portion, and thereafter, On the side opposite to the side where the bottom of the cylindrical cup body member is attached. The end portion is curled while being outwardly bent by a curling die in the same manner as described above to form a top flange portion to manufacture a paper cup, and thus, in the paper cup manufactured above, The contents are filled from the opening at the upper end, and then the lid is tightly adhered to the upper flange of the paper cup to seal the opening, thereby producing a paper cup package in which the contents are filled and packaged. As a result, it is possible to prevent cracks from occurring in the vapor deposition film of an inorganic oxide such as silicon oxide or aluminum oxide that constitutes the barrier layer, and to enable low-temperature sealing to eliminate the occurrence of roasting pinholes. As a result, it has an excellent barrier property to prevent the permeation of oxygen gas, water vapor, etc., avoids a seal failure, liquid leakage, etc. due to the occurrence of pinholes, prevents the deterioration of the contents, etc. Paper cups with excellent storability And it completed the present invention have found that it is possible to granulation.

That is, the present invention provides a paper cup comprising a tubular cup body member and a bottom member for sealing the bottom of the tubular cup body member, wherein the tubular cup body member and the bottom member are: At least an outermost layer, a paper base material, an adhesive layer composed of two polyolefin resin layers, and a barrier property composed of a vapor deposition film of an inorganic oxide and a gas barrier coating film provided on one surface of the base film. The present invention relates to a paper cup characterized by comprising a layer and a laminated material in which the innermost layer is sequentially laminated.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention described above will be described in more detail below with reference to the drawings. First, a configuration of a laminated material or the like constituting a paper cup according to the present invention will be described with reference to the drawings by exemplifying its 12 examples, and FIG. 1, FIG. 2, FIG.
And FIG. 4 is a schematic cross-sectional view showing a layer constitution of an example of a laminated material constituting the paper cup according to the present invention. Next, an example of the configuration of the paper cup according to the present invention will be described with reference to the drawings.
7 and 8 use the laminated material shown in FIG. 1 above,
It is a schematic block diagram which shows the structure of the paper cup in each box making process about the paper cup concerning this invention.

First, in the present invention, as the laminated material constituting the paper cup according to the present invention, as shown in FIGS. 1 and 2, at least the outermost layer 1, the paper base material 2, and two polyolefin resin layers. An adhesive layer 5 made of 3, 4 and a barrier layer 9 having a structure in which a vapor deposition film 7 of an inorganic oxide and a gas barrier coating film 8 are provided on one surface of a base film 6.
A laminated material A (FIG. 1) having a structure in which the innermost layer 10 is sequentially laminated, or a paper base material 2 excluding the outermost layer 1 in the laminated material A, and two polyolefin resin layers 3 4, an adhesive layer 5 composed of 4, a barrier layer 9 having a structure in which a vapor deposition film 7 of an inorganic oxide and a gas barrier coating film 8 are provided on one surface of a base film 6, and an innermost layer 1
The basic structure is a laminated material A ₁ (FIG. 2) having a structure in which 0s are sequentially laminated. Thus, in the present invention,
As a specific example of the laminated material constituting the paper cup according to the present invention, as shown in FIG. 3, at least an outermost layer 1, a paper base material 2, and a melt-extruded resin layer 3a obtained by melt-extruding and laminating a polyolefin resin. A two-layer polyolefin-based resin layer 3 of a polyolefin-based resin layer 4a previously laminated on the gas barrier coating film 8 constituting the barrier layer 9;
4, an adhesive layer 5 of 4, a barrier layer 9 having a structure in which a vapor deposition film 7 of an inorganic oxide and a gas barrier coating film 8 are provided on one surface of a base film 6, and an innermost layer 10 in that order. The laminated material A ₂ having a laminated structure can be exemplified. Further, in the present invention, for another specific example of the laminated material constituting the paper cup according to the present invention,
As shown in FIG. 4, at least the paper base material ₂ excluding the outermost layer 1, the melt-extruded resin layer 3a obtained by melt-extruding and laminating a polyolefin resin, and the barrier layer 9 are formed in the above-mentioned laminated material A ₂ . Adhesive layer 5 consisting of two polyolefin resin layers 3 and 4 of polyolefin resin layer 4a previously laminated on gas barrier coating film 8 and vapor deposition of inorganic oxide on one surface of base film 6. A barrier layer 9 composed of a film 7 and a gas barrier coating film 8, and
A laminated material A ₃ having a structure in which the innermost layer 10 is sequentially laminated can be exemplified. The above examples exemplify a few examples of the laminated material constituting the paper cup according to the present invention, and the present invention is not limited thereby.

For example, in the present invention, although not shown, in the structure of the laminated material as described above, the surfaces of the vapor deposition film of the inorganic oxide and the gas barrier coating film forming the barrier layer are the surfaces of the paper base material. Alternatively, it may be laminated so as to face any surface such as the surface of the innermost layer, but preferably, the components of the gas barrier coating film constituting the barrier layer are transferred to the contents side. Considering the viewpoint of preventing the above, it is desirable to stack the paper substrate so as to face it. Further, for example, in the present invention, although not shown, the vapor deposition film of the inorganic oxide constituting the barrier layer is not limited to a single-layer film consisting of one layer of the vapor deposition film of the inorganic oxide, but also the same or different inorganic oxides. It may be a multi-layer film or a composite film composed of two or more vapor-deposited films of the material. Furthermore, in the present invention, further, depending on the purpose of packaging the paper cup, the contents to be packed and packaged, the purpose of use, the use, etc. The base material can be arbitrarily laminated to design and produce a laminated material having various forms. Furthermore, in the present invention, it is desirable that the innermost layer has a large total thickness in order to improve the hermeticity and the like. Can be formed into a single layer or a multi-layer, and further, a polyolefin resin layer having a heat seal property due to low density polyethylene or the like can be provided between the barrier layer and the innermost layer. Is.

Next, in the present invention, the constitution of the paper cup according to the present invention will be explained by exemplifying one example thereof.
The case of using the laminated material A shown in FIG. 1 will be explained. As shown in FIG. 5, first, the laminated material A shown in FIG. 1 is used to make a body of a paper cup. A blank plate 11 is formed by punching in accordance with a required predetermined shape, for example, a truncated cone shape, and then the blank plate 11 is rolled into a tubular shape, and both side ends thereof are partially overlapped. The polymerized portion is subjected to flame treatment, or heat treatment such as hot air treatment, and the outermost layer and the innermost layer present in the polymerized portion, or the resin layer constituting the innermost layer is heated and melted, and A cylindrical cup body member B constituting a paper cup is manufactured by pressing a hot plate or the like to form a body seal portion 12 by sticking the body. On the other hand, as shown in FIG. 6, the same laminated material A that constitutes the blank plate 11 is used, and this is punched into a circular shape to manufacture the disc 13 that constitutes the bottom portion, Next, the outer peripheral portion of the circular plate 13 is formed into a cylindrical shape by standing up to manufacture the bottom member C having the standing up section 14.

Next, as shown in FIG. 7, the bottom member C also manufactured as described above is inserted into the cylindrical cup body member B manufactured as described above, and thereafter, the cylindrical cup body member B and the bottom part are prepared. The material C is blown with hot air or the like to the joint to heat and melt the outermost layer and the innermost layer present in the joint, or the resin layer forming the innermost layer. The tip portion 15 of the cylindrical cup body member B is not shown).
By bending inwardly and covering it with the upright forming part 14 constituting the bottom member C (see arrow P ₁ ), the tip forming part 15 of the tubular cup body member B and the upright forming part of the bottom member C. 14
By knurling the overlapped portion with and from the inner diameter side with a knurling (not shown), the cylindrical cup body member B and the bottom member C are closely adhered to each other to form the joint portion 16. Thus, the paper cup bottom portion D including the cylindrical cup body member B and the bottom member C is formed. Then, as shown in FIG. 8, the tip end portion 17 on the side opposite to the side on which the bottom member C of the cylindrical cup body member B is closely adhered to form the joint portion 16 is formed.
The similarly mosquito and the - force while bent outwardly by type for Le - (see P ₂₎ by Le, to form the upper flange portion 18, making paper cups E according to the present invention. Then, although not shown, the paper cup manufactured as described above is delivered to a maker or the like for filling the contents, and then the paper cup is supplied to a contents filling machine, and thereafter, the upper end of the paper cup is placed in the paper cup. To fill the contents from the opening of the paper cup, and then tightly adhere a lid or the like to the upper end flange portion of the paper cup to seal the opening, thereby producing a paper cup package in which the contents are filled and packaged. Is. Although not shown, usually, in order to prevent the permeation of the contents, the leakage of liquid, etc., the inner end surface of the body seal part forming the tubular cup body is, for example, subjected to a skive hemming treatment or the like. The end surface treatment is performed.
The above example is an example of the paper cup according to the present invention, and the present invention is not limited thereby. Of course, in the present invention, FIG.
Using the laminated materials shown in FIGS. 4 to 4, a paper cup similar to the above can be manufactured in the same manner as above.

Next, in the present invention, the materials constituting the paper cup and the like according to the present invention and the manufacturing method will be described in more detail. First, the outermost layer constituting the paper cup according to the present invention is, for example, melted by heat. However, a polyolefin resin having various heat-sealing properties that can be fused to each other, and the like can be used. In particular,
For example, low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear (linear) low-density polyethylene, ethylene-α · polymerized using a metallocene catalyst.
Olefin copolymer, 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,
Acid-modified polyolefin obtained by modifying a polyolefin resin such as methylpentene polymer, polybutene polymer, polyethylene or polypropylene with an unsaturated carboxylic acid such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid or itaconic acid. Resins such as resins, polyvinyl acetate resins, poly (meth) acrylic resins, polyvinyl chloride resins, and the like can be used. Thus, in the present invention, one or more of the above resins are used, and the resin is melt extruded using an extruder or the like, and, for example, anchored on one surface of the paper base material. By melt-extruding and laminating a melt-extruded resin layer via a coating agent layer or the like, or by using one or more kinds of the above-mentioned resins, a resin film or sheet is prepared in advance.
The outermost layer can be formed by producing a resin sheet and laminating the resin film or sheet on one surface of the paper substrate through a dry laminate through an adhesive layer for a laminate or the like. . In the present invention, the outermost layer has a thickness of about 5 to 200 μm, preferably 10 to 100 μm.
The position is desirable.

Next, in the present invention, as the paper base material constituting the paper cup according to the present invention, since this is a basic material constituting the paper cup, moldability, flex resistance, rigidity, waist, strength, etc. Can be used, for example, a strongly sized exposed or unbleached paper substrate, or
Various paper base materials such as pure white roll paper, kraft paper, paperboard, processed paper, and the like can be used. Further, in the present invention, as the paper base material, the basis weight is about 80 to 600 g.
/ M ² place, preferably a basis weight of about 100 to 450 g
It is possible to use a paper base material of the order of / m ² or the like. Further, in the present invention, as the paper base material, it is preferable to use curl resistant paper or the like in order to prevent curling or the like. In the present invention, desired print patterns such as characters, figures, patterns, symbols, etc. can be arbitrarily formed on the above-mentioned paper base material by an ordinary printing method.

Next, in the present invention, an adhesive layer composed of two polyolefin resin layers constituting the paper cup according to the present invention will be described. The adhesive layer includes a paper base material and a barrier layer. Is to be closely adhered. Thus, in the present invention, in the above-mentioned adhesive layer, as the polyolefin-based resin constituting the two polyolefin-based resin layers, for example, the above-mentioned outermost layer, which is melted by heat and fused to each other, is used. The obtained polyolefin resin having various heat seal properties, and the like can be used. Specifically, for example, low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear (linear) low-density polyethylene, ethylene-α-olefin copolymer polymerized using a metallocene catalyst, 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 An acid obtained by modifying a polyolefin resin such as a polymer, methylpentene polymer, polybutene polymer, polyethylene or polypropylene with an unsaturated carboxylic acid such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid or itaconic acid. Modified polyolefin resin, polyvinyl acetate resin, Li (meth) acrylic resin, polyvinyl chloride resin, to one free of resins and other like can be used two or more kinds.

Next, in the present invention, an adhesive layer composed of two polyolefin resin layers constituting the paper cup according to the present invention is formed by using one or more of the above polyolefin resins. In the present invention, first, a pretreatment such as ozone treatment, plasma treatment, corona treatment, etc. is first performed on the vapor-deposited film of the inorganic oxide and the gas barrier coating film forming the barrier layer. Or providing an anchor coating agent layer, and then melt-extruding and laminating one or more kinds of the above polyolefin-based resins using an extruder or the like to form a melt-extruded polyolefin-based resin layer. And forming the melt extruded polyolefin resin layer as one of the two polyolefin resin layers constituting the adhesive layer. . On the other hand, in the present invention, the paper substrate is made to face the surface of the melt-extruded polyolefin-based resin layer formed on the vapor deposition film of the inorganic oxide constituting the barrier layer and the gas barrier coating film as described above, and the interlayer In the same manner as above, if necessary, pretreatment such as ozone treatment, plasma treatment, corona treatment or the like, or by providing an anchor coating agent layer, one or more of the above polyolefin-based resins can be used. A melt-extruded polyolefin-based resin layer is formed by melt-extruding and laminating at least one kind of material using an extruder, and the melt-extruded polyolefin-based resin layer is the other polyolefin-based resin layer that constitutes the adhesive layer. is there. Thus, the adhesive layer is constituted by two polyolefin resin layers, one of which is the polyolefin resin layer and the other of which is the polyolefin resin layer, and in the present invention, the above-mentioned two-layer polyolefin resin layer. The paper base material and the barrier layer are closely adhered to each other via an adhesive layer composed of a resin layer.

By the way, when the paper base material and the barrier layer are closely adhered to each other, usually, a resin that can be melted by heat and fused to each other, specifically, low density polyethylene or the like is used and heated. While being melt-extruded by, is to be laminated through the melt-extruded resin layer, in this case, for example,
The low-density polyethylene must be heated to about 330 ° C to 350 ° C and melt-extruded. Therefore,
A heating temperature of about 330 ° C. to 350 ° C. acts on the vapor-deposited film of an inorganic oxide such as silicon oxide or aluminum oxide forming the barrier layer, and the vapor-deposited film of an inorganic oxide such as silicon oxide or aluminum oxide is cracked. Is likely to occur, oxygen gas,
This significantly deteriorates the barrier properties that prevent the permeation of water vapor and the like. Therefore, in the present invention, first, when forming a melt-extruded polyolefin-based resin layer as one polyolefin-based resin layer to be formed on the vapor deposition film and the gas barrier coating film of the inorganic oxide constituting the barrier layer Is preferably as thin as possible as the film thickness of the melt-extruded polyolefin-based resin layer. In consideration of pinhole resistance and the like, the film thickness is 30 μm or less, preferably 20 μm to 5 μm. And also
It is preferable to perform melt extrusion at a low temperature, and further perform pretreatment such as ozone treatment and perform melt extrusion lamination.

Further, in the present invention, when the melt extruded polyolefin resin layer as the other polyolefin resin layer for closely adhering the paper base material and the barrier layer is formed, it is melted at a low temperature as described above. It is preferable to perform extrusion and further pretreatment such as ozone treatment for melt extrusion lamination. In the present invention, the total thickness of the adhesive layer composed of the above two polyolefin resin layers is about 20 μm to 60 μm, preferably 20 μm to 5 μm.
It is desirable that the thickness is about 0 μm, and that the thickness of one of the polyolefin resin layers of the adhesive layer composed of the two polyolefin resin layers is thinner than the thickness of the other polyolefin resin layer. It is a thing. In the above, if the film thickness is less than 20 μm, the function tends to be lost, which is not preferable, and if the film thickness exceeds 60 μm, the moldability of the bottom portion and the top portion becomes extremely poor. It is not preferable. Further, in the present invention, during melt extrusion, by performing in-line corona treatment on the gas barrier coating film surface constituting the barrier layer, or by optionally performing pretreatment such as ozone treatment on the extrusion surface, The dense adhesion can be improved. In the present invention, silicon oxide, which is laminated through the melt-extruded melt-extruded resin layer as described above,
It is intended to prevent the occurrence of cracks or the like in the vapor-deposited film of an inorganic oxide such as aluminum oxide, and to prevent the deterioration of the barrier property which prevents the permeation of oxygen gas, water vapor and the like.

Next, in the present invention, the barrier layer constituting the paper cup according to the present invention will be described. First, as the base material film constituting the barrier layer, a vapor deposition film of an inorganic oxide is provided on the base material film. Therefore, it is possible to use a resin film or sheet having excellent properties in mechanical, physical, chemical, etc., and particularly having strength and toughness and heat resistance. it can. Specifically, in the present invention, as the substrate film, for example, polyethylene resin, polypropylene resin, cyclic polyolefin resin, fluorine resin, polystyrene resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile -Butadiene-styrene copolymer (ABS resin), polyvinyl chloride resin, fluorine resin, poly (meth) acrylic resin, polycarbonate resin, polyethylene terephthalate, polyethylene naphthalate Polyester resin such as, polyamide resin such as various nylon, polyimide resin, polyamide-imide resin, polyaryl phthalate resin, silicone
A film or sheet of various resins such as resin, polysulfone resin, polyphenylene sulfide resin, polyethersulfone resin, polyurethane resin, acetal resin, cellulose resin, etc. be able to. In the present invention, it is particularly preferable to use a polypropylene resin, polyester resin, or polyamide resin film or sheet.

In the present invention, as the film or sheet of the above various resins, for example, one or more of the above various resins are used, and the extrusion method, the cast molding method, the T die method, the cutting method. Film forming method such as the film forming method, the inflation method, and the like, or a method of forming a film of the above various resins alone, or a multilayer coextrusion film forming using two or more kinds of various resins. The method of forming a film or sheet of various resins by a method of forming a resin, and a method of using two or more kinds of resins and mixing them before forming a film. For example, various resin films or sheets obtained by uniaxially or biaxially stretching using a tenter system or a tuber system can be used. In the present invention, the film thickness of various resin films or sheets is preferably about 6 to 100 μm, more preferably about 9 to 50 μm.

It should be noted that when one or more of the above-mentioned various resins are used, and when forming a film, for example, the processability of the film, heat resistance, weather resistance, mechanical properties, dimensional stability,
Various plastic compounding agents and additives may be added for the purpose of improving and modifying antioxidative properties, slipperiness, releasability, flame retardancy, antifungal properties, electrical properties, strength, etc. You can
The addition amount thereof can be arbitrarily added from a very small amount to several tens of% depending on the purpose. In the above, as a general additive, for example, a lubricant, a crosslinking agent,
Antioxidants, ultraviolet absorbers, light stabilizers, fillers, antistatic agents, lubricants, anti-blocking agents, coloring agents such as dyes and pigments, and the like can be used, and further, modifying resins and the like. Can also be used.

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

Next, in the present invention, the vapor deposition film of the inorganic oxide constituting the barrier layer according to the present invention will be described. Examples of the vapor deposition film of the inorganic oxide include chemical vapor deposition or Those which can be produced by forming a single layer film composed of one layer of a vapor deposition film of an inorganic oxide or a multilayer film or composite film composed of two or more layers by physical vapor deposition or by using both of them together Is.

In the present invention, the inorganic oxide vapor deposition film by the above chemical vapor deposition method will be further described. As the inorganic oxide vapor deposition film by the chemical vapor deposition method,
For example, plasma chemical vapor deposition, thermal chemical vapor deposition,
Chemical vapor deposition methods such as photochemical vapor deposition (Chemica)
l Vapor Deposition method, CVD method)
And the like can be used to form a vapor deposition film of an inorganic oxide. In the present invention, specifically, on one surface of the base film, a monomer gas for vapor deposition such as an organic silicon compound is used as a raw material, and an inert gas such as argon gas or helium gas is used as a carrier gas. Further, a vapor deposition film of an inorganic oxide such as silicon oxide can be formed by using a low temperature plasma chemical vapor deposition method using a low temperature plasma generator or the like using oxygen gas or the like as the oxygen supply gas. . In the above, as the low temperature plasma generator, for example, a generator such as a high frequency plasma, a pulse wave plasma or a microwave plasma may be used, and therefore, in the present invention, a highly active and stable plasma is obtained. In order to
It is desirable to use a high frequency plasma generator.

Specifically, an example of the method for forming a vapor deposition film of an inorganic oxide by the above-mentioned low temperature plasma chemical vapor deposition method will be described by way of example. FIG. 1 is a schematic configuration diagram of a low temperature plasma chemical vapor deposition apparatus showing an outline of a method for forming an oxide vapor deposition film. As shown in FIG. 9 above, in the present invention, the vacuum chamber of the plasma enhanced chemical vapor deposition apparatus 21--
The base film 4 is unwound from the unwinding roll 23 arranged inside the roll 22, and the base film 4 is further fed to the auxiliary roll.
It is conveyed on the peripheral surface of the cooling / electrode drum 25 at a predetermined speed via the roller 24. Thus, in the present invention, a monomer for vapor deposition of oxygen gas, an inert gas, an organic silicon compound or the like from the gas supply devices 26 and 27, the raw material volatilization supply device 28 and the like.
Gas, etc. are supplied, the mixed gas composition for vapor deposition comprising them is not adjusted, the mixed gas composition for vapor deposition is introduced into the vacuum chamber 22 through the raw material supply nozzle 29, and the cooling The glow discharge plasma 30 is formed on the substrate film 4 conveyed on the peripheral surface of the electrode drum 25.
Plasma is generated by means of irradiation with the plasma to form a deposited film of an inorganic oxide such as silicon oxide. In the present invention, at this time, the cooling / electrode drum 25 is applied with a predetermined electric power from the power source 31 arranged outside the vacuum chamber-22, and the cooling / electrode drum 25 is provided near the cooling / electrode drum 25. The magnet 32 is arranged to promote the generation of plasma. Then, the substrate film 4 on which the vapor deposition film of the inorganic oxide such as silicon oxide is formed is wound on the winding roll 34 via the auxiliary roll 33, and the plasma chemical vapor phase according to the present invention is obtained. It is possible to form a vapor deposition film of an inorganic oxide by the growth method. In the figure, 35
Represents a vacuum pump. Needless to say, the above-mentioned exemplification is one example, and the present invention is not limited thereby. Although not shown, in the present invention, as the vapor deposition film of the inorganic oxide,
Not only one layer of the vapor deposition film of an inorganic oxide but also a multilayer film in which two or more layers are laminated may be used, and the materials to be used may be one kind or a mixture of two or more kinds, and may be different kinds. It is also possible to form a vapor deposition film of an inorganic oxide mixed with the material.

In the above, the inside of the vacuum chamber-22 is
The pressure is reduced by the empty pump 35, and the degree of vacuum is 1 × 10.^-1~ 1 x 1
0^-8Torr position, preferably vacuum degree 1 × 10^-3~ 1x
10 ^-7It is desirable to prepare it at the Torr position.
It Further, in the raw material volatilization supply device 28,
Gas supply device 26, 27 by volatilizing the organosilicon compound
Mixed with oxygen gas, inert gas, etc. supplied from
Vacuum chamber through the raw material supply nozzle 29
It is introduced in -22. In this case, mixed gas
The content of the organosilicon compound in the composition is about 1 to 40%, oxygen gas
The content of gas is about 10 to 70%, the content of inert gas
Can be in the range of about 10 to 60%, for example,
The mixing ratio of the organosilicon compound, oxygen gas and inert gas
It can be about 1: 6: 5 to 1:17:14.
On the other hand, the cooling / electrode drum 25 is provided with a predetermined power from the power source 31.
Since the voltage is applied, the original in the vacuum chamber-22
Between the opening of the material supply nozzle 29 and the cooling / electrode drum 25
A glow discharge plasma 30 is generated in the vicinity, and this glow discharge plasma 30 is generated.
The discharge plasma 30 is composed of one or more gas components in the mixed gas.
It is derived from the
The film 4 is conveyed at a constant speed, and the glow discharge plug
30, the base material film on the peripheral surface of the cooling / electrode drum 25 is
Form a vapor-deposited film of inorganic oxide such as silicon oxide on the rum 4.
Is what you can do. In addition, the vacuum
The degree of vacuum in the chamber is 1 x 10^-1~ 1 x 10^-FourTor
r position, preferably a vacuum degree of 1 × 10^-1~ 1 x 10^-2To
It is desirable to prepare it at the rr position, and a base film
The transportation speed of 4 is 10 to 300 m / minute, preferably,
It is desirable to prepare at 50 to 150 m / min.
is there.

The plasma chemical vapor deposition apparatus 2 described above is also used.
In 1, the formation of a vapor deposition film of an inorganic oxide such as silicon oxide is formed on the base film 4 in the form of a thin film in the form of SiO _x while oxidizing the plasma-generated source gas with oxygen gas. The formed vapor-deposited film of an inorganic oxide such as silicon oxide is a dense, flexible, continuous layer with few gaps, and therefore is a barrier of the vapor-deposited film of an inorganic oxide such as silicon oxide. The property is much higher than that of a vapor deposition film of an inorganic oxide such as silicon oxide formed by a conventional vacuum vapor deposition method or the like, and a sufficient barrier property can be obtained with a thin film thickness. Further, in the present invention, Si
The surface of the base film 4 is cleaned by the O _X plasma, and polar groups, free radicals, and the like are generated on the surface of the base film 4, so that a vapor-deposited film of an inorganic oxide such as silicon oxide is formed. It has an advantage that the close-adhesion property with the base film is high. Furthermore, the degree of vacuum during formation of a continuous film of an inorganic oxide such as silicon oxide is 1 as described above.
× 10 ⁻¹ to 1 × 10 ⁻⁴ Torr position, preferably 1 × 1
Since it is prepared at a position of 0 ⁻¹ to 1 × 10 ⁻² Torr, the degree of vacuum when forming a vapor deposition film of an inorganic oxide such as silicon oxide by a conventional vacuum vapor deposition method, 1 × 10 ⁻⁴ to 1 × 10. ^-5 Torr
Since the degree of vacuum is lower than that of the base film, the base film 4
It is possible to shorten the time for setting the vacuum state at the time of replacing the original fabric, easily stabilize the degree of vacuum, and stabilize the film forming process.

In the present invention, the vapor deposition film of silicon oxide formed by using a vapor deposition monomer gas such as an organic silicon compound causes a chemical reaction between a vapor deposition monomer gas such as an organosilicon compound and oxygen gas. The reaction product is closely adhered to one surface of the substrate film to form a dense, flexible thin film, which is usually represented by the general formula SiO _x (where X is
Represents a number of 0 to 2) and is a continuous thin film mainly composed of silicon oxide. Thus, as the above-mentioned vapor-deposited film of silicon oxide, from the viewpoint of transparency, barrier properties, etc., the general formula Si is used.
O _X (provided that, X represents represents. A number of 1.3 to 1.9) is intended is preferably a thin film mainly composed of vapor-deposited film of silicon oxide represented by. In the above, the value of X changes depending on the molar ratio of vapor deposition monomer gas and oxygen gas, the energy of plasma, etc. Generally, the smaller the value of X, the smaller the gas permeability, but the film itself. Becomes yellowish,
Poor transparency.

The silicon oxide vapor-deposited film contains silicon oxide as a main component, and at least one compound of carbon, hydrogen, silicon or oxygen, or at least one compound consisting of two or more of these elements. It is characterized in that it is composed of a vapor-deposited film containing types by chemical bonding or the like. For example,
When the compound having a C—H bond, the compound having a Si—H bond, or the carbon unit is in a graphite form, a diamond form, a fullerene form, or the like, a raw material organosilicon compound or a derivative thereof is further added. It may be contained by a chemical bond or the like. To give a specific example, CH
Hydrocarbon with ₃ sites, SiH ₃ silyl, Si
Examples thereof include hydrosilica such as H ₂ silylene and hydroxyl group derivatives such as SiH ₂ OH silanol. In addition to the above, the type, amount, etc. of the compound contained in the vapor deposition film of silicon oxide can be changed by changing the conditions in the vapor deposition process. The content of the above compound in the vapor deposited film of silicon oxide is 0.1 to 5
About 0%, preferably about 5 to 20% is desirable. In the above, if the content rate is less than 0.1%,
The impact resistance, spreadability, flexibility, etc. of the vapor-deposited film of silicon oxide are insufficient, and when it is bent, scratches, cracks, etc. easily occur, and it becomes difficult to stably maintain high barrier properties, On the other hand, if it exceeds 50%, the barrier property is deteriorated, which is not preferable. Further, in the present invention, it is preferable that the content of the above compound in the vapor-deposited film of silicon oxide be decreased in the depth direction from the surface of the vapor-deposited film of silicon oxide. On the surface of, the impact resistance and the like can be enhanced by the above compound and the like, while on the other hand, at the interface with the base film, since the content of the above compound is small, a base film and a vapor deposited film of silicon oxide are formed. It has an advantage that the tight adhesion property of is strong.

Therefore, in the present invention, the above-mentioned vapor-deposited film of silicon oxide is, for example, an X-ray photoelectron spectrometer (Xr
ay Photoelectron Spectros
copy, XPS), secondary ion mass spectrometer (Sec)
onary Ion Mass Spectrosc
The above physical properties are confirmed by performing elemental analysis of the vapor-deposited film of silicon oxide by using a method of analyzing by ion etching in the depth direction using a surface analyzer such as can do. Further, in the present invention, the film thickness of the vapor deposition film of silicon oxide is preferably 50 Å to 4000 Å, specifically, the film thickness is preferably 100 to 1000 Å. Then, in the above, 1000Å, and further 40
If it is thicker than 00Å, cracks and the like are likely to occur in the film, which is not preferable.
When it is less than 0Å, it is difficult to exert the effect of barrier property, which is not preferable. In the above, the film thickness can be measured by the fundamental parameter method using, for example, a fluorescent X-ray analyzer (model name, RIX2000 type) manufactured by Rigaku Co., Ltd. Further, in the above, as a means for changing the film thickness of the above-mentioned vapor-deposited film of silicon oxide, increasing the volumetric velocity of the vapor-deposited film, that is, a method of increasing the amount of monomer gas and oxygen gas or a vapor deposition rate is used. It can be done by a method of slowing down.

Next, in the above, as a vapor deposition monomer gas of an organic silicon compound or the like for forming a vapor deposition film of an inorganic oxide such as silicon oxide, for example, 1.1.3.3-tetramethyldisiloxane, Hexamethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxy Silane, phenyltrimethoxysilane, methyltriethoxysilane, octamethylcyclotetrasiloxane, etc. can be used. In the present invention, among the above-mentioned organic silicon compounds, it is preferable to use 1.1.3.3-tetramethyldisiloxane or hexamethyldisiloxane as a raw material for its handleability and formed continuous film. It is a particularly preferable raw material in view of the characteristics and the like. Further, in the above, as the inert gas, for example, argon gas, helium gas or the like can be used.

Next, in the present invention, the vapor deposition film of inorganic oxide by the physical vapor deposition method will be described in more detail. Examples of the vapor deposition film of inorganic oxide by the physical vapor deposition method include, for example, vacuum vapor deposition. Method, sputtering method,
Physical vapor deposition methods such as an ion plating method and an ion cluster beam method (Physical Vapor Deposition)
A deposition film of an inorganic oxide can be formed by using a position method or a PVD method). In the present invention, specifically, a metal oxide is used as a raw material, which is heated and vaporized, and this is vapor-deposited on one of the substrate films, or a metal or a metal is oxidized as a raw material. Film is deposited using an oxidation reaction deposition method in which oxygen is introduced to oxidize and deposit on one side of the base material film, and a plasma-assisted oxidation reaction deposition method in which the oxidation reaction is further supported by plasma. Can be formed. In the above, 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 specific example of the method of forming a thin film of an inorganic oxide by physical vapor deposition in the present invention is shown in FIG. 10. FIG. 10 is a schematic configuration diagram showing an example of a winding type vacuum vapor deposition apparatus. Is. As shown in FIG. 10, in the vacuum chamber-42 of the roll-up type vacuum vapor deposition apparatus 41,
The substrate film 4 fed from the unwinding roll 43 is guided to the cooled coating drum 46 via the guide rolls 44 and 45. Thus, the cooled core
The vapor deposition source 48 heated by the crucible 47, for example, metallic aluminum or aluminum oxide is evaporated on the base film 4 guided on the coating drum 46, and further, if necessary, an oxygen gas outlet. Oxygen gas or the like is spouted from 49, and while supplying this, the masks 50, 50
Via, for example, a vapor deposition film of an inorganic oxide such as aluminum oxide is formed, and then, in the above, for example, the base material film 4 on which the vapor deposition film of an inorganic oxide such as aluminum oxide is formed is guided by a guide roll. By sending out via 51, 52 and winding on the winding roll 53, a vapor deposition film of an inorganic oxide can be formed by the physical vapor deposition method according to the present invention. In addition, in the present invention, first, by using the winding type vacuum vapor deposition apparatus as described above,
Forming a vapor-deposited film of the inorganic oxide of the layer, and then forming a vapor-deposited film of the inorganic oxide on the vapor-deposited film of the inorganic oxide in the same manner, or winding the film as described above. Forming an inorganic oxide vapor deposition film composed of two or more layers by continuously connecting two of these using a vacuum vapor deposition apparatus and continuously forming an inorganic oxide vapor deposition film You can

In the above, as the vapor deposition film of the inorganic oxide, basically any thin film obtained by vapor deposition of a metal oxide can be used. For example, silicon (Si), aluminum (Al), magnesium (Mg). , Calcium (C
a), potassium (K), tin (Sn), sodium (N
It is possible to use a vapor deposition film of an oxide of a metal such as a), boron (B), titanium (Ti), lead (Pb), zirconium (Zr), or yttrium (Y). Thus, preferred are silicon (Si), aluminum (A
Examples thereof include vapor deposited films of metal oxides such as l).
Thus, the above-mentioned vapor-deposited film of metal oxide can be referred to as a metal oxide such as silicon oxide, aluminum oxide, and magnesium oxide, and the notation is, for example, SiO _x , AlO _x. , MO such as MgO _x
X (However, in the formula, M represents a metal element, and the value of X is
Each metal element has a different range. ). Further, the range of the value of X is silicon (S
i) is 0 to 2, aluminum (Al) is 0 to 1.
5, magnesium (Mg) is 0 to 1, calcium (C
a) is 0 to 1, potassium (K) is 0 to 0.5, tin (Sn) is 0 to 2, and sodium (Na) is 0 to 0.
5, boron (B) is 0 to 1, 5, titanium (Ti) is
0-2, lead (Pb) is 0-1, zirconium (Zr)
Can range from 0 to 2 and yttrium (Y) can range from 0 to 1.5. In the above, when X = 0,
It is a perfect metal and is not transparent and cannot be used at all, and the upper limit of the range of X is a completely oxidized value. In the present invention, generally, other than silicon (Si) and aluminum (Al), there are few examples used, and silicon (Si) is 1.0 to 2.0 and aluminum (A).
As l), those having a value in the range of 0.5 to 1.5 can be used. In the present invention, the film thickness of the vapor deposition film of the inorganic oxide as described above varies depending on the metal used, the type of the metal oxide, and the like, but is, for example, 50 to 20.
It is desirable to form it by arbitrarily selecting it in the range of 00Å, preferably in the range of 100 to 1000Å. Further, in the present invention, the metal used as the vapor deposition film of the inorganic oxide, or the metal oxide to be used, is used in one kind or in a mixture of two or more kinds. It is also possible to configure a vapor deposition film.

By the way, in the present invention, as the vapor deposition film of the inorganic oxide constituting the paper cup or the like according to the present invention, for example, both the physical vapor deposition method and the chemical vapor deposition method are used in combination, and the different inorganic oxides are used. It is also possible to use by forming a composite film composed of two or more layers of the above vapor deposition film. Therefore,
As a composite film composed of two or more layers of the above-mentioned vapor-deposited films of different kinds of inorganic oxides, first, by a chemical vapor deposition method, it is dense, flexible, and relatively free of cracks. A composite film composed of two or more layers, which is formed by providing a vapor-deposited film of an inorganic oxide capable of preventing generation, and then providing a vapor-deposited film of an inorganic oxide by physical vapor deposition on the vapor-deposited film of the inorganic oxide. It is desirable to form a vapor deposited film of an inorganic oxide composed of In the present invention, of course, contrary to the above, on the substrate film, first, the vapor deposition film of the inorganic oxide is provided by the physical vapor deposition method, and then the dense film is formed by the chemical vapor deposition method. It is also possible to provide an inorganic oxide vapor-deposited film that is highly flexible and can relatively prevent the occurrence of cracks, and to form an inorganic oxide vapor-deposited film that is a composite film composed of two or more layers. is there.

Next, in the present invention, the gas barrier coating film forming the barrier layer according to the present invention will be described. As the gas barrier coating film, at least a polyvinyl alcohol resin [hereinafter referred to as (A) component] is used. Say. ] And the general formula R ¹ _m M (OR ² ) _n ... (1)
(In the formula, M represents a metal atom, R ¹ is the same or different and represents an organic group having 1 to 8 carbon atoms, R ² is the same or different, and is an alkyl group having 1 to 5 carbon atoms or carbon number. 1 to
6 represents an acyl group or a phenyl group, and m and n
Each represents an integer of 0 or more, and m + n represents the valence of M. ), A metal alcoholate represented by the following formula, a hydrolyzate of the metal alcoholate, a condensate of the metal alcoholate,
At least one selected from the group consisting of the chelate compound of the metal alcoholate, the hydrolyzate of the chelate compound, and the metal acylate [hereinafter referred to as the component (B). ] A gas barrier coating film of a gas barrier composition containing and can be used. In the above, it is preferable that the gas barrier composition contains a nitrogen-containing organic solvent, and inorganic fine particles [hereinafter referred to as component (C)]. ] Is also preferable. Also, in the above,
As the component (B), it is possible to prepare a gas barrier composition by hydrolyzing the component (B) in water or a mixed solvent containing water and a hydrophilic organic solvent and then mixing the component (A) with the component. Is.

In the above gas barrier composition,
As the polyvinyl alcohol-based resin constituting the component (A), at least one selected from the group consisting of polyvinyl alcohol and ethylene / vinyl alcohol-based copolymers can be used. Of the above component (A), polyvinyl alcohol is generally obtained by saponifying polyvinyl acetate. The polyvinyl alcohol may be a partially saponified polyvinyl alcohol having an acetic acid group remaining of several tens of percent, a fully saponified polyvinyl alcohol having no acetic acid group remaining, or a modified polyvinyl alcohol having an OH group modified. It is not particularly limited. Specific examples of the polyvinyl alcohol include RS-110 (saponification degree = 99%, polymerization degree = 1,00), which is an RS polymer manufactured by Kuraray Co., Ltd.
0), Kuraray Poval LM-20SO manufactured by the same company (saponification degree = 40%, polymerization degree = 2,000), and Gohsenol NM-14 (saponification degree = 99) manufactured by Nippon Synthetic Chemical Industry Co., Ltd.
%, Degree of polymerization = 1,400) and the like can be used.
Further, among the component (A), the ethylene / vinyl alcohol copolymer is a saponified product of a copolymer of ethylene and vinyl acetate, that is, a product obtained by saponifying an ethylene-vinyl acetate random copolymer. The partial saponified product in which the acetic acid group remains several tens mol%, to the complete saponified product in which the acetic acid group remains only several mol% or the acetic acid group does not remain, is not particularly limited. From the viewpoint of gas barrier properties, the preferable saponification degree is 80 mol% or more,
More preferably, it is 90 mol% or more, and further preferably 9
It is 5 mol% or more. The content of repeating units derived from ethylene in the ethylene / vinyl alcohol copolymer (hereinafter, also referred to as "ethylene content") is usually 0 to 50 mol%, preferably 20 to 45 mol%. Specific examples of the ethylene / vinyl alcohol copolymer include Eval EP-F101 manufactured by Kuraray Co., Ltd. (ethylene content;
32 mol%), manufactured by Nippon Synthetic Chemical Industry Co., Ltd., Soarnol D2908 (ethylene content; 29 mol%) and the like can be used.

The melt flow index of the polyvinyl alcohol resin constituting the above component (A) is 210
1 to 20 g / 10 under a condition of ℃ and load of 21.168N
Min, preferably 1-18 g / 10 min. These polyvinyl alcohol resins constituting (A) may be used alone or in combination of two or more. Further, the polyvinyl alcohol-based resin constituting the component (A) itself has a gas barrier property,
Excellent weather resistance, organic solvent resistance, transparency, gas barrier property after heat treatment, etc. In addition, in the polyvinyl alcohol-based resin constituting the component (A), when the coating film obtained from the gas barrier composition of the present invention is cured, the hydroxyl group present in the repeating unit derived from polyvinyl alcohol will be described later ( By co-condensing with the component B) and / or the component (C), excellent coating performance can be brought about. The ratio of the component (A) in the gas barrier composition of the present invention is
10 to 10,000 with respect to 100 parts by weight of the component (B) described later.
0 parts by weight, preferably 20 to 5,000 parts by weight, and more preferably 100 to 1,000 parts by weight. 10
If it is less than 1 part by weight, the resulting coating film tends to be cracked and the gas barrier property is deteriorated, whereas if it exceeds 10,000 parts by weight, the gas coating property is deteriorated under high humidity, which is not preferable. Is.

Next, as the component (B) used in the present invention, the metal alcoholate, the hydrolyzate of the metal alcoholate and the condensate of the metal alcoholate represented by the above-mentioned general formula (1). A chelate compound of the metal alcoholate,
At least one selected from the group of hydrolysates of the chelate compounds and metal acylates can be used,
As the component (B), only one kind thereof may be used, or a mixture of any two or more kinds may be used. It should be noted that, as the hydrolyzate of the metal alcoholate, it is not necessary that all OR ² contained in the metal alcoholate be hydrolyzed, and for example, only one of them is hydrolyzed, or two or more thereof May be hydrolyzed, or a mixture thereof. Further, the above-mentioned metal alcoholate condensate is one in which M-OH groups of the hydrolyzate of metal alcoholate are condensed to form an M-O-M bond, but in the present invention, the M-OH group is used. Does not need to be all condensed, and is a concept including a mixture of a small part of M-OH groups, a mixture of those having different degrees of condensation, and the like. Further, the chelate compound of the metal alcoholate is a metal alcoholate, β-diketones, β-ketoesters, hydroxycarboxylic acid, hydroxycarboxylic acid salt, hydroxycarboxylic acid ester,
It is obtained by a reaction with at least one compound selected from keto alcohol and amino alcohol. Among these compounds, it is preferable to use β-diketones or β-ketoesters, and specific examples thereof include:
Acetylacetone, methyl acetoacetate, ethyl acetoacetate, acetoacetate-n-propyl, acetoacetate-i-propyl, acetoacetate-n-butyl, acetoacetate-sec-
Butyl, acetoacetic acid-t-butyl, 2,4-hexane-
Examples thereof include dione, 2,4-heptane-dione, 3,5-heptane-dione, 2,4-octane-dione, 2,4-nonane-dione, and 5-methyl-hexane-dione. Further, the hydrolyzate of the above chelate compound, like the hydrolyzate of the above metal alcoholate,
It is not necessary that all the OR ² groups contained in the chelate compound be hydrolyzed, and for example, only one of them is hydrolyzed, or two or more of them are hydrolyzed.
Alternatively, it may be a mixture thereof. In the present invention, the component (B) is considered to function to form a cocondensate with the component (A).

As the metal atom represented by M in the above general formula (1), zirconium, titanium and aluminum can be mentioned as preferable ones, and titanium is particularly preferable. The monovalent organic group having 1 to 8 carbon atoms of R ¹ differs depending on whether the compound represented by the general formula (1) is a metal alcoholate or a metal acylate. In the case of metal alcoholate, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-
Alkyl groups such as butyl group, i-butyl group, sec-butyl group, t-butyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group; acetyl group, propionyl group, butyryl group Acyl groups such as valeryl group, benzoyl group and trioyl group; vinyl group, allyl group, cyclohexyl group, phenyl group, glycidyl group,
In addition to (meth) acryloxy group, ureido group, amide group, fluoroacetamide group, isocyanate group, etc.,
Substituted derivatives of these groups and the like can be mentioned. R
The substituent in the substituted derivative of ¹ , for example, a halogen atom, a substituted or unsubstituted amino group, a hydroxyl group, a mercapto group, an isocyanate group, a glycidoxy group, 3,
4-epoxycyclohexyl group, (meth) acryloxy group, ureido group, ammonium base and the like can be mentioned. However, the carbon number of R ¹ including these substituted derivatives is 8 or less including the carbon atoms in the substituent.
When the metal acylate is used, R ¹ has 1 carbon atom.
Examples of the monovalent organic group of to 8 include acyloxyl groups such as an acetoxyl group, a propionyloxyl group, a butyryloxyl group, a valeryloxyl group, a benzoyloxyl group and a trioyloxyl group. When two R ¹ 's are present in the general formula (1), they may be the same or different.

Examples of the alkyl group having 1 to 5 carbon atoms for R ² include, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, t-butyl group. Group, n-pentyl group and the like, and examples of the acyl group having 1 to 6 carbon atoms include acetyl group, propionyl group, butyryl group, valeryl group and caproyl group. A plurality of R ^{2 s} in the general formula (1) may be the same or different from each other.

Among these components (B), specific examples of metal alcoholates and chelate compounds of metal alcoholates include (a). Tetra-n-butoxyzirconium, tri-n
-Butoxy ethyl acetoacetate zirconium, di-n-butoxy bis (ethyl acetoacetate) zirconium, n-butoxy tris (ethyl acetoacetate) zirconium, tetrakis (n-propyl acetoacetate) zirconium, tetrakis (acetylacetoacetate) Zirconium compounds such as zirconium and tetrakis (ethylacetoacetate) zirconium;

(B). Tetra-i-propoxytitanium, tetra-n-butoxytitanium, tetra-t-butoxytitanium, di-i-propoxy bis (ethylacetoacetate) titanium, di-i-propoxy.
Bis (acetylacetate) titanium, di-i-propoxy bis (acetylacetonato) titanium, di-n-butoxy bis (triethanolaminato) titanium, dihydroxybislactatertotitanium, dihydroxytitanium lactate, tetrakis (2 −
Titanium compounds such as ethylhexyloxy) titanium;

(C). Tri-i-propoxy aluminum, di-i-propoxy ethyl acetoacetate aluminum, di-i-propoxy acetyl acetonate aluminum, i-propoxy bis (ethyl acetoacetate) aluminum, i-propoxy bis (acetyl acetonate) ) Aluminum, tris (ethylacetoacetate) aluminum, tris (acetylacetonato) aluminum, monoacetylacetonate / bis (ethylacetoacetate) aluminum, and other aluminum compounds; Among these metal alcoholates and chelate compounds of metal alcoholates, preferred are tri-n-butoxyethyl acetoacetate zirconium, di-i-propoxy bis (acetylacetonato) titanium, di-n-butoxy. Examples thereof include bis (triethanolaminato) titanium, dihydroxy bislactetatotitanium, di-i-propoxy ethylacetoacetate aluminum and tris (ethylacetoacetate) aluminum, and particularly preferred compounds are di-i-propoxy. Titanium compounds such as bis (acetylacetonato) titanium, di-n-butoxy bis (triethanolaminato) titanium, and dihydroxy bislactatertotitanium.

Specific examples of the metal acylate include:
Dihydroxy titanium dibutyrate, di-i-propoxy titanium diacetate, di-i-propoxy titanium dipropionate, di-i-propoxy titanium dimaloneate, di-i-propoxy titanium dibenzoylate, di -N-butoxy zirconium diacetate, di-i-propylaluminum monomaloniate and the like can be mentioned, and a particularly preferred compound is dihydroxy.
Titanium compounds such as titanium dibutyrate and di-i-propoxy titanium diacetate. These (B) components may be used alone or in combination of two or more.

As the component (B), the viscosity of the coating liquid does not change with time and is easy to handle. It is preferable to use a decomposed product. In this case, the amount of water used is R ¹ _m M (OR
² ) 0.1 to 1 mol of the compound represented by _n (1)
It is 1000 mol, preferably 0.5 to 500 mol. In the case of a mixed solvent, the mixing ratio of water and the hydrophilic organic solvent is water / hydrophilic organic solvent = 10 to 90/90 to 10.
(Weight ratio), preferably 30 to 70/70 to 30, and more preferably 40 to 60/60 to 40.

Next, the gas barrier composition of the present invention preferably contains inorganic fine particles as the component (C). The above-mentioned inorganic fine particles are particulate inorganic substances having an average particle diameter of 0.2 μm or less and substantially not containing carbon atoms, and examples thereof include metals or silicon oxides, metals or silicon nitrides, and metal borides. The method for producing the inorganic fine particles includes, for example, a gas phase method for obtaining silicon oxide by hydrolysis of silicon tetrachloride in a flame of oxygen and hydrogen, a liquid phase method for obtaining ion exchange of sodium silicate, and a silica gel mill. Examples of the production method include a solid-phase method obtained by pulverization by, for example, but are not limited to these methods.

Specific examples of compounds include SiO ₂ , A
l ₂ O ₃ , TiO ₂ , WO ₃ , Fe, ZnO, NiO,
RuO ₂ , CdO, SnO ₂ , Bi ₂ O ₃ , 3Al ₂ O
₃ · O ₂ , Sn-In ₂ O ₃ , Sb-In ₂ O ₃ , Co
Oxides such as FeOx, Si, Fe ₄ N, AlN, Ti
N, ZrN, TaN and other nitrides, Ti ₂ B, ZrB,
Examples thereof include borides such as TaB ₂ and W ₂ B. Also,
Examples of the form of the inorganic fine particles include powder, colloid or sol dispersed in water or an organic solvent, but are not limited thereto. Among these, in order to obtain excellent coating performance by co-condensing with the component (A) and / or the component (B), colloidal silica, colloidal alumina, alumina sol, tin sol, zirconium sol, pentoxide is preferable. Colloidal oxides having a hydroxyl group on the particle surface such as antimony sol, cerium oxide sol, zinc oxide sol, and titanium oxide sol are used. The average particle size of the inorganic fine particles is 0.2 μm or less, preferably 0.1 μm
When the average particle size is more than 0.2 μm, the gas barrier property may be deteriorated from the viewpoint of the denseness of the film.

The ratio of the component (C) in the composition of the present invention is
The total amount of the components (A) and (B) is 100 parts by weight, preferably 10 to 900 parts by weight, particularly preferably 20 to 400 parts by weight. In the above, 900
When it exceeds the weight part, the gas barrier property of the obtained coating film may be deteriorated.

Next, in the present invention, the purpose of hardening the gas barrier coating film of the gas barrier composition of the present invention faster is to facilitate the formation of a cocondensate of the components (A) and (B). The (D) curing accelerator may be used for the purpose, and it is more effective to use the (D) curing accelerator together in order to cure at a relatively low temperature and obtain a more dense coating film. .

Examples of the (D) curing accelerator include inorganic acids such as hydrochloric acid; alkali metal salts such as naphthenic acid, octylic acid, nitrous acid, sulfurous acid, aluminic acid and carbonic acid; sodium hydroxide, potassium hydroxide and the like. Alkaline compounds; Alkyl titanic acid, phosphoric acid, methanesulfonic acid, p-toluenesulfonic acid, phthalic acid and other acidic compounds; ethylenediamine, hexanediamine, diethylenetriamine,
Triethylenetetramine, tetraethylenepentamine,
Piperidine, piperazine, metaphenylenediamine, ethanolamine, triethylamine, various modified amines used as curing agents for epoxy resins, γ-aminopropyltriethoxysilane, γ- (2-aminoethyl)-
Aminopropyltrimethoxysilane, γ- (2-aminoethyl) -aminopropylmethyldimethoxysilane, γ
- amine compounds such as anilino _{trimethoxysilane, (C 4 H 9) 2} Sn (OCOC 11 H 23) 2 (C
_{4 H 9) 2 Sn (OCOCH} = CHCOOCH 3) 2,
(C ₄ H ₉ ) ₂ Sn (OCOCH = CHCOOC
₄ H ₉ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (OCOC
₁₁ H ₂₃ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (OCOCH = CHC
OOCH ₃ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (OCOCH = C
HCOOC ₄ H ₉ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (OCOC
H = CHCOOC ₈ H ₁₇ ) ₂ , Sn (OCOCC
Carboxylic acid type organotin compounds such as ₈ H ₁₇ ) ₂ ; (C _{4
H 9) 2 Sn (SCH 2} COOC 8 H 17) 2, (C 4 H
₉ ) ₂ Sn (SCH ₂ COOC ₈ H ₁₇ ) ₂ , (C
₈ H ₁₇ ) ₂ Sn (SCH ₂ COOC ₈ H ₁₇ ) ₂ , (C _{8
H 17) 2 Sn (SCH 2} CH 2 COOC 8 H 17) 2,
_{(C 8 H 17) 2 Sn} (SCH 2 COOC 8 H 17) 2,
_{(C 8 H 17) 2 Sn} (SCH 2 COOC 12 H 25) 2, Mercaptide type organotin compounds such as; Sulfide type organotin compounds such as;

(C ₄ H ₉ ) ₂ SnO, (C ₈ H ₁₇ ) ₂ S
nO or _{(C 4 H 9) 2 SnOH} 17) organotin oxide and ethyl silicate, such as ₂ SnO,, dimethyl maleate, diethyl maleate, organic tin compounds such as the reaction product of an ester compound such as dioctyl phthalate, etc. Is used. The proportion of these (D) curing accelerators in the gas barrier composition is usually 0.5 with respect to 100 parts by weight of the solid content of the gas barrier composition of the present invention.
-50 parts by weight, preferably 0.5-30 parts by weight.

Further, the above-mentioned β-diketones and / or β-ketoesters can be added to the gas barrier composition of the present invention as a stability improver. That is, the action of controlling the condensation reaction between the component (A) and the component (B) by coordinating with the metal atom in the metal alcoholate present in the gas barrier composition as the component (B). Therefore, it is considered that the gas barrier composition obtained has the function of improving the storage stability. The amount of β-diketones and / or β-ketoesters used is preferably 2 mol or more, and more preferably 3 to 20 mol, based on 1 mol of the metal atom in the component (B).

The gas barrier composition of the present invention is usually obtained by dissolving and dispersing the above components (A) to (D) and optionally the above optional components in water and / or a hydrophilic organic solvent. Here, specific examples of the hydrophilic organic solvent include methanol, ethanol, n-propanol, i-propanol, n-butyl alcohol, and se.
c-butyl alcohol, tert-butyl alcohol,
Carbon number 1 such as diacetone alcohol, ethylene glycol, diethylene glycol, triethylene glycol
~ 8 saturated aliphatic monohydric alcohol or dihydric alcohol; 1 to 8 carbon atoms such as ethylene glycol monobutyl ether and ethylene glycol monoethyl ether acetate
Saturated aliphatic ether compounds; C1-8 saturated aliphatic dihydric alcohol ester compounds such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate; N, N-dimethyl Acetamide, N, N-dimethylformamide, γ-
Nitrogen-containing compounds (nitrogen-containing organic solvents) such as butyrolactone, N-methylpyrrolidone, pyridine; sulfur-containing compounds such as dimethyl sulfoxide; hydroxycarboxylic acids or hydroxycarboxylic acid esters such as lactic acid, methyl lactate, ethyl lactate, salicylic acid, and methyl salicylate. And so on. Of these, preferred are methanol, ethanol, n-propanol, i-
Saturated aliphatic monohydric alcohol having 1 to 8 carbon atoms such as propanol, n-butyl alcohol, sec-butyl alcohol and tert-butyl alcohol; N, N-dimethylacetamide, N, N-dimethylformamide, γ-
Examples thereof include nitrogen-containing compounds (nitrogen-containing organic solvents) such as butyrolactone, N-methylpyrrolidone and pyridine.

These water and / or hydrophilic organic solvent are more preferably used as a mixture of water and a hydrophilic organic solvent. The preferred composition of the solvent is water / saturated aliphatic monohydric alcohol having 1 to 8 carbon atoms and water / nitrogen-containing compound (nitrogen-containing organic solvent). More preferably, it is water / saturated aliphatic monohydric alcohol having 1 to 8 carbon atoms / nitrogen-containing compound (nitrogen-containing organic solvent). By mixing the nitrogen-containing organic solvent, it is possible to obtain a good coating film having a transparent appearance in thin film coating.

The amount of water and / or hydrophilic organic solvent used is preferably such that the total solid concentration of the gas barrier composition is 6%.
It is used so as to be 0% by weight or less. For example, when it is used for the purpose of forming a thin film, it is usually 5 to 40% by weight, preferably 10 to 30% by weight, and when it is used for the purpose of forming a thick film, it is usually 20 to 50% by weight. %, Preferably 30 to 45% by weight. When the total solid content concentration of the gas barrier composition exceeds 60% by weight, the storage stability of the composition tends to decrease. The proportion of the nitrogen-containing organic solvent is usually 1 to 70% by weight, preferably 5 to 50% by weight, based on the total amount of the solvent.

The organic solvent is preferably water and / or a hydrophilic organic solvent as described above, but in addition to the hydrophilic organic solvent, for example, aromatic hydrocarbons such as benzene, toluene, xylene, tetrahydrofuran, dioxane, etc. Ethers, ketones such as acetone and methyl ethyl ketone, and esters such as ethyl acetate and butyl acetate can also be used.

As described above, the gas barrier composition of the present invention is obtained by mixing the above-mentioned components (A) to (B) and optionally the above-mentioned optional components in water and / or a hydrophilic organic solvent, Preferably, it is obtained by hydrolyzing and / or condensing the above-mentioned component (A) and component (B), and optionally component (C) in water and / or a hydrophilic organic solvent. At this time, the reaction conditions include a temperature of 20 to 100 ° C., preferably 30 to 80 ° C., and a time of 0.1 to 20 hours, preferably 1 to 10 hours. The weight average molecular weight of the obtained gas barrier composition is a polymethylmethacrylate conversion value by a general GPC method,
Usually, 500 to 1,000,000, preferably 1,000 to 30
In many cases.

The gas barrier composition of the present invention contains
A filler may be added and dispersed separately in order to develop various properties such as coloring of the resulting coating film, thickening of the film, prevention of ultraviolet ray transmission to the base, provision of corrosion resistance, and heat resistance. However, the filler excludes the component (C). Examples of the filler include water-insoluble pigments such as organic pigments and inorganic pigments, or other than pigments, particulate, fibrous or scale-like metals and alloys, and oxides, hydroxides, carbides, and nitrides thereof. , Sulfide and the like. Specific examples of this filler include iron, copper, aluminum, nickel, silver, zinc, ferrite, carbon black, stainless steel, silicon dioxide, titanium oxide, aluminum oxide and chromium oxide in the form of particles, fibers or scales. , Manganese oxide, iron oxide, zirconium oxide, cobalt oxide,
Synthetic mullite, aluminum hydroxide, iron hydroxide, silicon carbide, silicon nitride, boron nitride, clay, diatomaceous earth,
Slaked lime, gypsum, talc, barium carbonate, calcium carbonate, magnesium carbonate, barium sulfate, bentonite,
Mica, zinc green, chrome green, cobalt green, viridian, guinea green, cobalt chrome green, schele green, green soil, manganese green, pigment green, ultramarine blue, dark blue, pigment green, rock ultramarine, cobalt blue, cerulean blue, boric acid Copper, molybdenum blue, copper sulfide, cobalt purple, Mars purple,
Manganese purple, pigment violet, lead suboxide, calcium leadate, zinc yellow, lead sulfide, chrome yellow, loess,
Cadmium yellow, strontium yellow, titanium yellow, litharge, pigment yellow, cuprous oxide, cadmium red, selenium red, chrome vermillion, red iron oxide, zinc white, antimony white, basic lead sulfate, titanium white, lithopone, lead silicate, Zircon oxide, tungsten white, lead zinc white, bunchison white, lead phthalate, manganese white, lead sulfate, graphite, bone black, diamond black, thermatomic black, vegetable black, potassium titanate whiskers, molybdenum disulfide, etc. To be

The average particle size or average length of these fillers is usually 50 to 50,000 nm, preferably 100.
~ 5,000 nm. The proportion of the filler in the composition is
With respect to 100 parts by weight of the total solid content of components other than the filler, preferably 0.1 to 300 parts by weight, more preferably 1
~ 200 parts by weight.

The gas barrier composition of the present invention contains
In addition, known dehydrating agents such as methyl orthoformate, methyl orthoacetate, and tetraethoxysilane, various surfactants, silane coupling agents other than the above, titanium coupling agents, dyes, dispersants, thickeners, leveling It is also possible to add additives such as agents.

In preparing the gas barrier composition of the present invention, the above-mentioned components (A) to (B), preferably (A).
~ A composition containing the component (C) may be prepared. Preferably, the component (B) is hydrolyzed in water or a mixed solvent containing water and a hydrophilic organic solvent, and then the component (A) is added. Mix. In this case, the viscosity of the gas barrier composition does not change with time, and a gas barrier composition having excellent handleability can be obtained. Specific examples of the method for preparing the gas barrier composition of the present invention using the component (C) include the following methods. The component (B) used in these preparation methods may be hydrolyzed in advance in water or a mixed solvent containing water and a hydrophilic organic solvent. After adding the component (C) to the component (A) dissolved in water and / or a hydrophilic organic solvent, (B)
How to add ingredients. After adding the component (C) to the component (A) dissolved in water and / or a hydrophilic organic solvent,
A method of adding the component (B) and performing hydrolysis and / or condensation. The component (C) is added to the component (B) dissolved in water and / or a hydrophilic organic solvent to cause hydrolysis and / or
Alternatively, a method in which condensation is carried out and then the component (A) is added. Water and / or hydrophilic organic solvent (A) ~
A method in which the component (C) is added all at once and dissolved / dispersed. Alternatively, a method of performing hydrolysis and / or condensation after that.

Thus, in the present invention, the gas barrier composition prepared as described above is used, and this composition is applied onto the above-mentioned vapor deposition film of an inorganic oxide to form a gas barrier coating film. be able to. In the present invention, the inorganic oxide vapor deposition film and the gas barrier coating film, for example,
By forming a chemical bond, hydrogen bond, or coordination bond by hydrolysis / co-condensation reaction, the adhesion between the vapor deposition film of the inorganic oxide and the gas barrier coating film is improved, and by the synergistic effect of the two layers, It is possible to exert a better gas barrier effect. Examples of the method of applying the gas barrier composition of the present invention include a roll coating method such as a gravure coater, a spray coating method, a spin coating method, a dipping method, a brush method, a bar code method, and a coating method such as an applicator method. The gas barrier coating film of the present invention having a dry film thickness of 0.01 to 30 μm, preferably 0.1 to 10 μm can be formed by coating once, and under normal environment, it is 50 to 300 ° C., preferably 70-200
At a temperature of 0.005 to 60 minutes, preferably 0.
By heating and drying for 01 to 10 minutes, condensation is performed, and the gas barrier coating film of the present invention can be formed. Further, if necessary, a primer agent or the like can be applied in advance on the vapor-deposited film of the inorganic oxide when applying the gas barrier composition of the present invention.

Next, in the present invention, the innermost layer constituting the paper cup according to the present invention will be described. The innermost layer can be formed by using the same material as the outermost layer. Specifically, for example, a polyolefin resin having various heat seal properties that can be melted by heat and fused to each other, and the like can be used. Thus, in the present invention, as the innermost layer, for example, low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear (linear) low-density polyethylene, ethylene-polymerized using a metallocene catalyst
α-olefin copolymer, 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 Acid modification of polyolefin resins such as methyl pentene polymer, polybutene polymer, polyethylene or polypropylene with unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid and itaconic acid A resin such as a polyolefin resin, a polyvinyl acetate resin, a poly (meth) acrylic resin, a polyvinyl chloride resin, or the like can be used.

Thus, in the present invention, one or more of the above resins are used and melt-extruded using an extruder or the like to obtain, for example, an anchor coating agent layer or the like. By melt-extruding and laminating a melt-extruded resin layer, or by using one or more of the above-mentioned resins in advance to produce a resin film or sheet from the resin. The innermost layer can be formed by laminating the film or sheet of (1) and (2) on the dry laminate through the adhesive layer for the laminate. Further, in the present invention, one or more of the above resins are used, and they are also used as a coextrusion laminated resin layer composed of two or more layers obtained by melt coextrusion with a coextruder or the like. In this case, in order to prevent the occurrence of cracks and the like in the vapor deposition film of the inorganic oxide, increase the film thickness of the resin layer on the side in contact with the contents, the film thickness of the other resin layer It is preferable that the thickness of the other resin layer be about 10 to 30 μm, preferably about 20 μm. Furthermore, in the present invention,
In order to prevent the occurrence of cracks and the like in the vapor deposition film of the inorganic oxide, by using the resin forming the innermost layer described above, after forming a melt-extruded resin layer with a film thickness as thin as possible, on it,
The innermost layer can be formed by using one or more kinds of the above-mentioned resins forming the innermost layer and providing a coextruded resin layer using a coextruder or the like. In the present invention, the thickness of the innermost layer is preferably about 5 to 200 μm, and more preferably 10 to 100 μm.

By the way, in the present invention, the resin forming the innermost layer is usually a resin that can be melted by heat and fused to each other, specifically, low-density polyethylene or linear (linear) It is constructed by using polyolefin resin such as low density polyethylene, but in that case, low density polyethylene or linear (linear)
The seal temperature of the polyolefin resin layer such as low-density polyethylene is about 320 ° C to 350 ° C, which is an extremely high seal temperature, so that pinholes are generated and the seal is generated.
It is easy to cause a defective product, liquid leakage, etc.
Therefore, in the present invention, attention is paid to an ethylene-α-olefin copolymer polymerized by using a metallocene catalyst having a low-temperature sealing property, and the innermost layer is formed by the copolymer.
It is preferable to enable a low temperature seal of about 0 ° C to 300 ° C, prevent the occurrence of pinholes, and avoid defective seals, liquid leakage, and the like. Furthermore, the ethylene-α-olefin copolymer polymerized by using a metallocene catalyst has an advantage that the propagation of breakage is small and the impact resistance is improved because it has adhesiveness, and the innermost layer is always Since it is in contact with the contents, it is also effective for preventing deterioration of the environmental stress cracking resistance.
Further, in the present invention, it is also possible to blend another resin to the ethylene-α-olefin copolymer polymerized using a metallocene catalyst, for example, by blending an ethylene-butene copolymer or the like, slightly, Although the heat resistance is poor and the seal stability tends to deteriorate in a high temperature environment, there is an advantage that the tearability is improved and it contributes to easy opening. In the present invention, particularly when an innermost layer composed of an ethylene-α-olefin copolymer layer polymerized using a metallocene catalyst is used, a low temperature heat seal property is possible when a paper cup is manufactured. It has the advantage that

Examples of the ethylene-α-olefin copolymer polymerized by using the above metallocene catalyst include:
A catalyst obtained by combining a metallocene complex such as a catalyst obtained by combining zirconocene dichloride and methylalumoxane with an alumoxane, that is, an ethylene-α-olefin copolymer obtained by copolymerizing ethylene and an α-olefin using a metallocene catalyst. Polymers can be used. The above-mentioned metallocene catalyst is also called a single-site catalyst because the active site is non-uniform and is called a multi-site catalyst, while the active site is uniform (hereinafter referred to as a single-site catalyst). , Metallocene catalysts have the same meaning as single-site catalysts.) Specifically, as an ethylene-α / olefin copolymer polymerized using a metallocene catalyst, Mitsubishi Chemical Co., Ltd., trade name "Kaneru", Mitsui Petrochemical Industry Co., Ltd., trade name "Evolu"-", Exxon Chemical (EXXO, USA
NCHEMICAL's product name "Exact (EX
ACT ", Dow Chemical, USA
Product name “Affinity- (AFFIN
It is possible to use an ethylene-α-olefin copolymer polymerized with a metallocene catalyst such as TY) and a trade name “ENGAGE”. Thus, in the present invention, the innermost layer composed of the ethylene-α-olefin copolymer layer polymerized using the metallocene catalyst as described above may be, for example, an anchor coating agent on the surface of the barrier layer. Melt extrusion laminating method of laminating via a layer or the like, or dry laminating method of laminating via a laminating adhesive layer or the like
It can be formed by using a normal laminating method such as a gating method.
In the present invention, the film thickness of the innermost layer is about 10 μm to 300 μm, preferably 20 μm to 100 μm.
The m position is desirable.

The ethylene-α.olefin copolymer polymerized using the above metallocene catalyst will be described in more detail. Specifically, for example, a catalyst obtained by combining a metallocene-based transition metal compound and an organoaluminum compound,
That is, an ethylene-α-olefin copolymer obtained by copolymerizing ethylene and α-olefin using a metallocene catalyst (including a so-called Kaminski catalyst) can be used. The metallocene catalyst may be supported on an inorganic material for use. In the above, examples of the metallocene-based transition metal compound include, for example, I
Transition metals selected from Group VB, specifically titanium (Ti), zirconium (Zr), hafnium (Hf)
1 or 2 of cyclopentadienyl group, substituted cyclopentadienyl group, indenyl group, substituted indenyl group, tetrahydroindenyl group, substituted tetrahydroindenyl group, fluorenyl group or substituted fluorenyl group, Alternatively, two of these groups are linked by a covalent bond, and a hydrogen atom, an oxygen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, etc.
Group, acetylacetonate group, carbonyl group, nitrogen molecule, oxygen molecule, Lewis base, substituent containing a silicon atom,
Those having a ligand such as unsaturated hydrocarbon can be used. Further, in the above, as the organoaluminum compound, alkylaluminum, chain-like or cyclic aluminoxane, or the like can be used. Here, examples of the alkyl aluminum include triethyl aluminum, triisobutyl aluminum, dimethyl aluminum chloride, diethyl aluminum chloride, methyl aluminum dichloride, ethyl aluminum dichloride, dimethyl aluminum fluoride, diisobutyl aluminum hydride, diethyl aluminum sesquichloride. Etc. can be used. The chain or cyclic aluminoxane can be produced, for example, by bringing alkylaluminum into contact with water. For example, it can be produced by adding alkylaluminum at the time of polymerization and then adding water, or by reacting crystallization water of a complex salt or adsorbed water of an organic / inorganic compound with alkylaluminum. Then again, in the above,
Examples of the inorganic substance supporting the metallocene catalyst include, for example,
Silica gel, zeolite, silicon earth, etc. can be used.

Next, in the above, as the polymerization method,
For example, it can be carried out by various polymerization methods such as bulk polymerization, solution polymerization, suspension polymerization and gas phase polymerization. Further, the above-mentioned polymerization may be carried out by any method such as a batch system or a continuous system. In the above, the polymerization conditions include a polymerization temperature and -1.
The temperature is from 00 to 250 ° C., the polymerization time is from 5 minutes to 10 hours, the reaction pressure is from atmospheric pressure to 300 Kg / cm ² . Further, in the present invention, α which is a comonomer copolymerized with ethylene
-As olefins, for example, propylene, 1-butene, 3-methyl-1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, decene and the like can be used. The above-mentioned α-olefins may be used alone or in combination of two or more. In addition, the mixing ratio of the above α / olefin is, for example, 1 to 50% by weight, preferably 10 to 30%.
It is preferably set to wt%. Thus, in the present invention, ethylene-polymerized using the above metallocene catalyst
The physical properties of the α-olefin copolymer have, for example, a molecular weight of 5
× 10 ^{3 to} 5 × 10 ⁶ , density, 0.890 to 0.930
g / cm ³ , melt flow rate [MFR], 0.1
It is about 50 g / 10 minutes. In the present invention, the ethylene-α-olefin copolymer polymerized using the above metallocene catalyst includes, for example, antioxidants, ultraviolet absorbers, antistatic agents, antiblocking agents, lubricants (fatty acid amides, etc.). ), Flame retardants, inorganic or organic fillers, dyes, pigments, etc. can be optionally added and used.

Further, in the present invention, the innermost layer composed of the ethylene-α-olefin copolymer layer polymerized by the metallocene catalyst is the ethylene-α-olefin copolymer copolymerized by the metallocene catalyst as described above. Co-extruded laminated resin layer of coalesce and polyolefin resin such as low-density polyethylene and linear low-density polyethylene, and further ethylene-α / olefin-based polymerized by metallocene catalyst constituting the co-extruded laminated resin layer A coextrusion laminated resin layer having a resin layer as an innermost layer can be used. In the above, as a method for forming the coextrusion laminated resin layer, a T-die coextrusion method or the like can be used.
The layer structure is composed of a coextruded laminated resin layer composed of two or more layers, and the thickness of each resin layer may be arbitrarily adjusted within the range of about 2 to 30 μm. In particular, the film thickness of the resin layer on the side opposite to the resin layer on the side in contact with the content is 30 μm or less, preferably about 10 to 20 μm.

In the present invention, as the material for forming the laminated material constituting the paper cup according to the present invention, for example, low density polyethylene, medium density polyethylene, high density polyethylene having a barrier property against water vapor, water, etc. Chain low density polyethylene, polypropylene, film or sheet of resin such as ethylene-propylene copolymer, or polyvinylidene chloride resin having barrier property against oxygen, water vapor, etc., polyvinyl alcohol resin, A film or sheet of a resin such as an ethylene-vinyl alcohol copolymer, MXD polyamide resin, polynaphthalene terephthalate resin, or the like, a colorant such as a pigment is added to the resin, and other desired additives are added. Films or sheets of various colored resins having a light-shielding property obtained by kneading and forming a film are also used. It is possible. These materials are
One kind or a combination of two or more kinds can be used. The thickness of the above-mentioned film or sheet is arbitrary, but is usually about 5 μm to 300 μm, and further,
10 μm to 100 μm is desirable.

In the present invention, the packaging container is usually subjected to severe physical and chemical conditions, so that the packaging material constituting the packaging container is required to have strict packaging suitability. Therefore, various conditions such as deformation prevention strength, drop impact strength, pinhole resistance, heat resistance, sealability, quality maintainability, workability, hygiene, etc. are required. , A material satisfying the above various conditions can be arbitrarily selected and used, and specifically, for example, low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, Ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ionomer-resin, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid or methacrylic acid copolymer, Cylpentene 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 resin, polyvinyl alcohol -Based resin, saponified ethylene-vinyl acetate copolymer, fluorine-based resin,
Any known film or sheet of a known resin such as a diene resin, a polyacetal resin, a polyurethane resin, nitrocellulose, etc. can be selected and used. In the present invention, the film or sheet may be unstretched, uniaxially or biaxially stretched, or the like. The thickness is arbitrary, but it can be selected from the range of several μm to 300 μm and used. Further, in the present invention, as the film or sheet, extrusion film formation,
The film may be any film such as an inflation film and a coating film. In addition, for example, a film such as cellophane, synthetic paper, or the like can be used.

Next, in the present invention, a desired printed pattern layer can be formed between any of the layers forming the laminated material constituting the paper cup according to the present invention.
As the above-mentioned printed pattern layer, for example, on the above-mentioned barrier coating film, a usual gravure ink composition, an offset ink composition, a letterpress ink composition, a screen ink composition, and other ink compositions are used. For example, by using a gravure printing method, an offset printing method, a letterpress printing method, a silk screen printing method, or another printing method, for example, by forming a desired printed pattern consisting of characters, figures, patterns, symbols, etc. Can be configured.
Regarding the above ink composition, as a vehicle constituting the ink composition, for example, polyolefin resin such as polyethylene resin, chlorinated polypropylene resin, poly (meth) acrylic resin, polyvinyl chloride resin, polyvinyl acetate, etc. Resin, vinyl chloride-vinyl acetate copolymer, polystyrene resin, styrene-butadiene copolymer, vinylidene fluoride resin, polyvinyl alcohol resin, polyvinyl acetal resin, polyvinyl butyral resin, polybutadiene resin, polyester resin Resin, polyamide resin, alkyd resin, epoxy resin, unsaturated polyester resin, thermosetting poly (meth) acrylic resin, melamine resin, urea resin, polyurethane resin, phenol resin, xylene resin , Maleic acid resin, Fibrous resins such as rocellulose, ethyl cellulose, acetylbutyl cellulose, ethyloxyethyl cellulose, rubber resins such as chlorinated rubber and cyclized rubber, petroleum resins, natural resins such as rosin and casein, linseed oil, soybean oil, etc. A mixture of one or more kinds of fats and oils and other resins can be used. In the present invention, one or more kinds of the above-mentioned vehicles are used as a main component, and one or more kinds of coloring agents such as dyes and pigments are added thereto, and if necessary,
Fillers, stabilizers, plasticizers, antioxidants, light stabilizers such as UV absorbers, dispersants, thickeners, desiccants, lubricants, antistatic agents, cross-linking agents, and other additives are optionally added. ,solvent,
It is possible to use an ink composition having various forms obtained by sufficiently kneading with a diluent or the like.

In the present invention, a method for producing a laminated material using the above materials will be described below.
As such a method, a method of laminating a usual packaging material, for example, a wet lamination method, a dry lamination method, a solventless dry lamination method, an extrusion lamination method, a T-die extrusion molding method, The extrusion lamination method, the inflation method, the coextrusion inflation method, and the like can be used.
In the present invention, therefore, pretreatment such as corona treatment, plasma treatment, ozone treatment, and the like can be optionally performed, if necessary, when performing the above-mentioned lamination, and, for example, isocyanate. -(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 A known anchor coating agent such as an adhesive for laminate of a system or the like, an adhesive for laminate and the like can be optionally used.

In the present invention, the method for producing the laminated material according to the present invention will be specifically described. For example, a dry lamination method of laminating via a laminating adhesive layer using a laminating adhesive, or melt extrusion. It can be performed by an extrusion lamination method or the like in which the resin is laminated via a melt-extruded resin layer made of an adhesive resin. In the above, examples of the laminating adhesive include, for example, one-component or two-component curing or non-curing type vinyl-based, (meth) acrylic-based, polyamide-based, polyester-based, polyether-based, polyurethane-based, epoxy-based adhesives. , Solvent type such as rubber type and others, aqueous type, or
Emulsion type adhesives for laminating can be used. As a coating method of the above-mentioned laminating adhesive, for example, a direct gravure roll coating method, a gravure roll coating method, a kiss coating method, a reverse roll coating method, a Fonten method, a transfer roll coating method and the like can be applied. The coating amount is preferably 0.1 to 10 g /
m ² (dry state), more preferably 1 to 5 g / m
² (dry state). In addition, for example, an adhesion promoter such as a silane coupling agent can be optionally added to the laminating adhesive.

In the above, as the melt-extruded adhesive resin, the heat-sealable resin forming the heat-sealable resin layer described above can be used in the same manner, and low-density polyethylene, particularly linear low-density polyethylene It is preferable to use acid-modified polyethylene. The thickness of the melt-extruded resin layer formed by the melt-extruded adhesive resin is preferably about 5 to 100 μm, and more preferably
It is about 10 to 50 μm. In the present invention, when it is necessary to obtain a stronger adhesive strength when performing the above-mentioned lamination, an adhesion improver such as an anchor coat agent may be coated. As the anchor coating agent, for example, an organic titanium-based anchor coating agent such as an alkyl titanate, an isocyanate-based anchor coating agent,
A polyethyleneimine-based anchor coating agent, a polybutadiene-based anchor coating agent, and other various water-based or oil-based anchor coating agents can be used. In the present invention, the anchor coating agent is coated by roll coating, gravure coating, knife coating, dip coating, spray coating, or other coating method,
An anchor coat agent layer can be formed by drying a solvent, a diluent and the like. The coating amount of the anchor coating agent is preferably about 0.1 to 5 g / m ² (dry state).

Next, in the present invention,
As the paper cup according to the present invention, for example, any shape such as a triangular, quadrangular, pentagonal, hexagonal, or other rectangular shape, or a cylindrical paper can such as a round shape can be manufactured. You can Further, in the present invention, the paper cup according to the present invention is filled with various articles such as various foods and drinks, chemicals such as adhesives and adhesives, general merchandise such as cosmetics and pharmaceuticals, and others. Is something that can be done. Thus, in the present invention, the liquid paper container according to the present invention is, in particular, a liquid seasoning for, for example, a liquor, a juice such as a fruit juice beverage, a mineral water, a soy sauce, a sauce, a soup and the like. Fee, or curry, stew, soup,
It is useful as a packaging container for filling and packaging various other liquid food and drink.

[0078]

EXAMPLES The present invention will be described more specifically with reference to examples. Example 1 (1). A biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was used, and this film was attached to a delivery roll of a plasma enhanced chemical vapor deposition apparatus, and then the above biaxially stretched polyethylene terephthalate film was placed under the following conditions. A 200 Å-thick vapor-deposited film of silicon oxide was formed on the corona-treated surface of the glass film. (Deposition conditions) Deposition surface; Corona treatment surface Introduction gas amount; Hexamethyldisiloxane: Oxygen gas: Helium = 1.0: 3.0: 3.0 (unit: slm) Vacuum degree in vacuum chamber; 6 × 10 ⁻⁶ mBar Vacuum degree in vapor deposition chamber; 2 to 5 × 10 ⁻³ mBar Cooling / electrode drum power supply; 10 kW Line speed; 100 m / min Next, the above-mentioned 200 Å film thickness of silicon oxide vapor deposition film Immediately after the formation of the silicon oxide, a glow discharge plasma generator was used on the surface of the deposited film of silicon oxide, and the power was 9 kw, oxygen gas (O ₂ ): argon gas (Ar) = 7.0: 2.5 ( Unit: slm) is used, and mixed gas pressure is 6
× 10 ^-5 Torr, oxygen / at a processing speed of 420 m / min
Argon mixed gas plasma treatment was performed to form a plasma-treated surface in which the surface tension of the deposited surface of silicon oxide was improved by 54 dyne / cm or more. (2). On the other hand, in a reactor equipped with a reflux condenser and a stirrer,
100 parts of tetra-i-propoxy titanium and 70 parts of acetylacetone were added and stirred at 60 ° C. for 30 minutes to obtain a titanium chelate compound. The purity of this reaction product was 75%. Next, as the component (A), an ethylene / vinyl alcohol copolymer [Nippon Gosei Kagaku KK, trade name,
Soarnol D2935, saponification degree; 98% or more, ethylene content; 29 mol%, melt flow index; 35
g / 10 minutes] 5% water / n-propyl alcohol solution (water / n-propyl alcohol weight ratio = 40/60) 1
00 parts, 2 parts of the titanium chelate compound prepared above, 16.8 parts of n-propyl alcohol, and 11.2 of water.
The parts were mixed, and the component (B) hydrolyzed at 55 ° C. for 4 hours was mixed at 40 ° C. and stirred for 2 hours to obtain a gas barrier composition of the present invention. Next, the plasma-treated surface formed in (1) above is coated with the gas barrier composition prepared above by the gravure roll coating method, and then heat-treated at 120 ° C. for 2 minutes. A gas barrier coating film having a thickness of 0.5 g / m ² (dry state) was formed to produce a barrier layer. (3). Then, on the surface of the gas barrier coating film of the barrier layer produced in the above (2), a two-component curing type anchor anchor coating agent [Takelac A3210 / Takelac Co., Ltd., trade name] Takenet A3075, amount of coat:
1 g / m ² (dry state)] was applied with a gravure coater and passed through a drying furnace, and then the surface of the anchor coating agent layer was subjected to ozone treatment while the extrusion temperature was raised to 280 ° C. hand,
A low-density polyethylene resin [density, 0.919, melt index (MI), 9.0] was used, and this was extrusion-coated to form a low-density polyethylene resin layer having a thickness of 20 μm. Next, one surface of the cup base paper having a basis weight of 300 g / m ² is made to face the surface of the low-density polyethylene resin layer of the barrier layer produced above, and an in-line corona treatment or an ozone treatment is performed, and the layers are put between the layers. Low density polyethylene resin [density, 0.923, melt index (MI), 3.7] is used, and this is extruded film thickness 20μ
While extruding to m, they were extrusion-laminated to bond the cup base paper and the barrier layer together. Furthermore, on the surface of the biaxially stretched polyethylene terephthalate film having a thickness of 12 μm, which constitutes the barrier layer laminated with the above-mentioned cup base paper, a two-component curing type ester-based anchor coating agent [Takeda Yakuhin Kogyo Co., Ltd. Company made, product name, Takeraku A32
10 / Takenet A3075, coating amount: 1 g / m
² (dry state)] is applied by a gravure coater and passed through a drying oven, and then a low density polyethylene resin [density, 0.923, melt index ( M.I), 3.7] was used, and this was extrusion-coated to form a low-density polyethylene resin layer having a thickness of 20 μm. Further, after the corona treatment discharge treatment is applied to the other surface of the cup base paper laminated with the barrier layer as described above, the low density polyethylene resin [density, 0.
923, melt index (MI), 3.7] was used, and this was extrusion-coated to form a low-density polyethylene resin layer having a thickness of 20 μm. Next, on the surface of the low-density polyethylene resin layer having a thickness of 20 μm extruded on the surface of the biaxially stretched polyethylene terephthalate film having a thickness of 12 μm, which constitutes the barrier layer laminated with the above cup base paper, A low-density polyethylene resin [density, 0.923, melt index (MI), 3.7] is used, and this is extrusion-coated to form a low-density polyethylene resin layer having a thickness of 40 μm. A laminated material according to the invention was produced. (4). Then, using the laminated material manufactured as described above, a frustoconical blank plate for forming the body portion of the paper cup from the laminated material was punched, and further subjected to end face treatment such as skive hemming. Next, the above blank plate is rolled into a tubular shape, and its both end portions are partially overlapped, and the polymerized portion is subjected to flame treatment, or hot treatment such as hot air treatment, to the above polymerized portion. A low-density polyethylene resin layer that forms the outermost layer and the innermost layer that are present is melted by heating, and then pressed by a hot plate or the like to form a cylinder seal by forming a cylinder seal, and a cylinder that forms a paper cup. A cup-shaped body was produced. On the other hand, in the same manner as above, the laminated material produced above is used, and this is punched into a circular shape to produce a disk that constitutes the bottom, and then the outer peripheral portion of the disk is erected in a cylindrical shape. Molded to produce a bottom having upright moldings. Next, in the tubular cup body produced above, the bottom produced in the same manner is inserted, and thereafter, the tubular cup body and the bottom are produced by blowing hot air or the like onto the joint portion thereof. The low-density polyethylene resin layer forming the outermost layer and the innermost layer existing in the joint portion is heated and melted, and then the tip of the tubular cup body is bent inward by a curling die to form the above-mentioned bottom portion. By covering with a knurling from the inner diameter side, the overlapped portion of the tip of the cylindrical cup body and the erected molding of the bottom is covered by a knurling. The cup-shaped cup body and the bottom portion were closely adhered to each other to form a joint, and the paper cup bottom portion including the tubular cup body portion and the bottom portion was formed. Thereafter, the tip end portion on the side opposite to the side where the bottom portion of the tubular cup body portion is tightly adhered to form the joint portion is bent outward by a curling die in the same manner as described above. And a top flange portion was formed to manufacture a paper cup having a capacity of 500 cc according to the present invention. (5). Next, from the opening at the upper end of the paper cup produced above, fill with miso, then lay perchmate paper on it, further put an oxygen scavenger, and then, at the upper end of the opening of the paper cup. A lid member was tightly adhered to the flange portion and the opening was sealed to produce a miso package. In the above-prepared miso package, generation of roasting pinholes, etc. was not observed, and further, excellent barrier properties against oxygen gas, water vapor, etc., and excellent aroma retention, and alteration of its contents was observed. In addition, it was excellent in laminate strength, endured distribution in the market, and excellent in storage and storage.

Example 2 (1). The barrier layer produced in the above Example 1 is used in the same manner, and in the same manner as in the above Example 1, the two-component curing type ester anchor coater is applied to the surface of the gas barrier coating film of the barrier layer. Gravure coater (trade name, Takelac A3210 / Takenet A3075, coat amount: 1 g / m ² (dry state)) manufactured by Takeda Pharmaceutical Co., Ltd.
And then passed through a drying oven, and then the surface of the anchor-coating agent layer is subjected to ozone treatment while the extrusion temperature is 280 ° C.
, A low-density polyethylene resin [density, 0.919, melt index (MI), 9.0] was used, and this was extrusion-coated to form a low-density polyethylene resin layer having a thickness of 20 μm. . Next, the surface of the low-density polyethylene resin layer of the barrier layer produced above is opposed to one surface of the cup base paper having a basis weight of 300 g / m ² , and in-line corona treatment or ozone treatment is performed, and the layers are separated between the layers. Low density polyethylene resin [density, 0.923, melt index (MI), 3.7] is used, and this is extruded film thickness 2
While extruding to 0 μm, laminating both of them,
The above cup base paper and the barrier layer were laminated together. Further, a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm, which constitutes a barrier layer laminated with the above-mentioned cup base paper.
Two-component curing type ester-based anchor coating agent [Takeda Pharmaceutical Co., Ltd., trade name, Takelac A3210 / Takenet A3075, coating amount: 1 g /
m ² (dry state)] was applied with a gravure coater and passed through a drying oven, and then a low density polyethylene resin [density, 0.923, melt index] was applied to the surface of the anchor coating agent layer. (M.I), 3.7], which is extruded
To form a low-density polyethylene resin layer having a thickness of 20 μm. Further, after the corona treatment discharge treatment is applied to the other surface of the cup base paper laminated with the barrier layer as described above, the low-density polyethylene resin [density,
0.923, melt index (MI), 3.7]
Was used, and this was extrusion-coated to form a low-density polyethylene resin layer having a thickness of 20 μm. Next, on the surface of the low-density polyethylene resin layer having a thickness of 20 μm extruded on the surface of the biaxially stretched polyethylene terephthalate film having a thickness of 12 μm, which constitutes the barrier layer laminated with the above cup base paper, Low density polyethylene resin [Density, 0.923,
Melt index (MI) 3.7] and ethylene-α-olefin copolymer resin polymerized using a metallocene catalyst [density, 0.907, melt index (M.I.
I), 11.0], and two coextrusion laminated resin layers of a low density polyethylene resin layer and an ethylene-α-olefin copolymer resin layer polymerized using a metallocene catalyst. And the film thickness of the low-density polyethylene resin layer is 15 μm, and the film thickness of the ethylene-α / olefin copolymer resin layer polymerized by using a metallocene catalyst is 20 μm to form an innermost layer of 55 μm in total. Then, the laminated material according to the present invention was manufactured. (2). Then, using the laminated material produced above, a paper cup having a capacity of 500 cc according to the present invention was produced in the same manner as in Example 1 above, and was further used for miso packaging. Manufactured body. In the above-prepared miso package, generation of roasting pinholes, etc. was not observed, and further, excellent barrier properties against oxygen gas, water vapor, etc., and excellent aroma retention, and alteration of its contents was observed. In addition, it was excellent in laminate strength, endured distribution in the market, and excellent in storage and storage.

Example 3 (1). The barrier layer produced in the above Example 1 is used in the same manner, and in the same manner as in the above Example 1, the two-component curing type ester anchor coater is applied to the surface of the gas barrier coating film of the barrier layer. Gravure coater (trade name, Takelac A3210 / Takenet A3075, coat amount: 1 g / m ² (dry state)) manufactured by Takeda Pharmaceutical Co., Ltd.
And then passed through a drying oven, and then the surface of the anchor-coating agent layer is subjected to ozone treatment while the extrusion temperature is 280 ° C.
, A low-density polyethylene resin [density, 0.919, melt index (MI), 9.0] was used, and this was extrusion-coated to form a low-density polyethylene resin layer having a thickness of 20 μm. . Next, the surface of the low-density polyethylene resin layer of the barrier layer produced above is opposed to one surface of the cup base paper having a basis weight of 300 g / m ² , and in-line corona treatment or ozone treatment is performed, and the layers are separated between the layers. Low density polyethylene resin [density, 0.923, melt index (MI), 3.7] is used, and this is extruded film thickness 2
While extruding to 0 μm, laminating both of them,
The above cup base paper and the barrier layer were laminated together. Further, after corona treatment discharge treatment is applied to the other surface of the cup base paper laminated with the barrier layer as described above, the low density polyethylene resin [density, 0.92
3, melt index (MI), 3.7] was used, and this was extrusion-coated to form a low-density polyethylene resin layer having a thickness of 20 μm. Then, on the surface of the biaxially stretched polyethylene terephthalate film having a thickness of 12 μm which constitutes the barrier layer laminated with the above-mentioned cup base paper, a two-component curing type ester anchor coating agent [Takeda Yakuhin Kogyo Co., Ltd. Product name, Takerak A3210 / Takenet A
3075, coating amount: 1 g / m ² (dry state)] was applied by a gravure coater and passed through a drying oven, and then the surface of the anchor coating agent layer was subjected to ozone treatment. However, a low-density polyethylene resin [density, 0.923, melt index (MI), 3.7] is used, and this is extruded and coated to form a low-density polyethylene resin layer having a thickness of 60 μm. The innermost layer was formed to manufacture the laminated material according to the present invention. (2). Then, using the laminated material produced above, a paper cup having a capacity of 500 cc according to the present invention was produced in the same manner as in Example 1 above, and was further used for miso packaging. Manufactured body. In the above-prepared miso package, generation of roasting pinholes, etc. was not observed, and further, excellent barrier properties against oxygen gas, water vapor, etc., and excellent aroma retention, and alteration of its contents was observed. In addition, it was excellent in laminate strength, endured distribution in the market, and excellent in storage and storage.

Example 4 (1). As a base film, a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm is used.
The biaxially stretched polyethylene terephthalate film was mounted on a delivery roll of a roll-up type vacuum vapor deposition device, and then it was fed out, and the corona-treated surface of the biaxially stretched polyethylene terephthalate film was coated with aluminum. Was used as a vapor deposition source while supplying oxygen gas, and a vacuum vapor deposition method by an electron beam (EB) heating system was used to form a vapor deposition film of aluminum oxide having a film thickness of 200 Å under the following vapor deposition conditions. (Deposition conditions) Degree of vacuum in deposition chamber: 2 × 10 ⁻⁴ mbar Degree of vacuum in winding chamber: 2 × 10 ⁻² mbar Electronic beam power: 25 kW Film transfer speed: 240 m / min Deposition surface Next, a plasma-treated surface was formed on the aluminum oxide vapor-deposited film surface in the same manner as in Example 1 immediately after forming the aluminum oxide vapor-deposited film having a thickness of 200Å. (2). On the other hand, in a reactor equipped with a reflux condenser and a stirrer,
100 parts of tetra-i-propoxy titanium and 70 parts of acetylacetone were added and stirred at 60 ° C. for 30 minutes to obtain a titanium chelate compound. The purity of this reaction product was 75%. Next, as the component (A), an ethylene / vinyl alcohol copolymer [Nippon Gosei Kagaku KK, trade name,
Soarnol D2935, saponification degree; 98% or more, ethylene content; 29 mol%, melt flow index; 35
g / 10 minutes] 5% water / n-propyl alcohol solution (water / n-propyl alcohol weight ratio = 40/60) 1
00 parts, 2 parts of the titanium chelate compound prepared above, 16.8 parts of n-propyl alcohol, and 11.2 of water.
The parts were mixed, and the component (B) hydrolyzed at 55 ° C. for 4 hours was mixed at 40 ° C. and stirred for 2 hours to obtain a gas barrier composition of the present invention. Next, the plasma-treated surface formed in (1) above is coated with the gas barrier composition prepared above by the gravure roll coating method, and then heat treated at 120 ° C. for 2 minutes. hand,
A gas barrier coating film having a thickness of 0.5 g / m ² (dry state) was formed to produce a barrier layer. (3). Next, using the barrier layer produced above, in the same manner as in Example 1 above, a two-component curing type ester-based anchor coating agent was applied to the surface of the gas barrier coating film of the barrier layer. [Takeda Pharmaceutical Co., Ltd., trade name, Takelac A3210 / Takenet A3075, coat amount: 1 g /
m ² (dry state)] was applied by a gravure coater and passed through a drying oven, and then the surface of the anchor coating agent layer was subjected to ozone treatment at an extrusion temperature of 280 ° C. A low density polyethylene resin [density, 0.919, melt index (MI), 9.0] was used, and this was extrusion coated to form a low density polyethylene resin layer having a thickness of 20 μm. Next, the surface of the low-density polyethylene resin layer of the barrier layer produced above is opposed to one surface of the cup base paper having a basis weight of 300 g / m ² , and in-line corona treatment or ozone treatment is performed, and the layers are separated between the layers. Low density polyethylene resin [density, 0.923, melt index (M.
I), 3.7] was used to extrude both of them while extruding them to an extruded film thickness of 20 μm, and the above cup base paper and the barrier layer were bonded together. Furthermore, a thickness of 12 which constitutes the barrier layer laminated with the above cup base paper
On the surface of the biaxially stretched polyethylene terephthalate film having a thickness of 2 μm, a two-component curing type ester anchor coating agent [Takelac A3210 /, manufactured by Takeda Pharmaceutical Co., Ltd.]
Takenet A3075, coating amount: 1 g / m ² (dry state)] was applied by a gravure coater and passed through a drying oven, and then the surface of the anchor coating agent layer was coated with a low coating. Density polyethylene resin [density, 0.923, melt index (M.
I), 3.7], which is extrusion coated to a thickness of 2
A 0 μm low density polyethylene resin layer was formed. Also,
After the corona discharge treatment is applied to the other surface of the cup base paper laminated with the barrier layer, the low density polyethylene resin [density, 0.923, melt index (M.I. ). 3.7] was used, and this was extrusion-coated to form a low-density polyethylene resin layer having a thickness of 20 μm. Next, on the surface of the low-density polyethylene resin layer having a thickness of 20 μm extruded on the surface of the biaxially stretched polyethylene terephthalate film having a thickness of 12 μm, which constitutes the barrier layer laminated with the above cup base paper, A low-density polyethylene resin [density, 0.923, melt index (MI), 3.7] is used, and this is extrusion-coated to form a low-density polyethylene resin layer having a thickness of 40 μm. A laminated material according to the invention was produced. (4). Then, using the laminated material manufactured as described above, a frustoconical blank plate for forming the body portion of the paper cup from the laminated material was punched, and further subjected to end face treatment such as skive hemming. Next, the above blank plate is rolled into a tubular shape, and its both end portions are partially overlapped, and the polymerized portion is subjected to flame treatment, or hot treatment such as hot air treatment, to the above polymerized portion. A low-density polyethylene resin layer that forms the outermost layer and the innermost layer that are present is melted by heating, and then pressed by a hot plate or the like to form a cylinder seal by forming a cylinder seal, and a cylinder that forms a paper cup. A cup-shaped body was produced. On the other hand, in the same manner as above, the laminated material produced above is used, and this is punched into a circular shape to produce a disk that constitutes the bottom, and then the outer peripheral portion of the disk is erected in a cylindrical shape. Molded to produce a bottom having upright moldings. Next, in the tubular cup body produced above, the bottom produced in the same manner is inserted, and thereafter, the tubular cup body and the bottom are produced by blowing hot air or the like onto the joint portion thereof. The low-density polyethylene resin layer forming the outermost layer and the innermost layer existing in the joint portion is heated and melted, and then the tip of the tubular cup body is bent inward by a curling die to form the above-mentioned bottom portion. By covering with a knurling from the inner diameter side, the overlapped portion of the tip of the cylindrical cup body and the erected molding of the bottom is covered by a knurling. The cup-shaped cup body and the bottom portion were closely adhered to each other to form a joint, and the paper cup bottom portion including the tubular cup body portion and the bottom portion was formed. Thereafter, the tip end portion on the side opposite to the side where the bottom portion of the tubular cup body portion is tightly adhered to form the joint portion is bent outward by a curling die in the same manner as described above. And a top flange portion was formed to manufacture a paper cup having a capacity of 500 cc according to the present invention. (5). Next, from the opening at the upper end of the paper cup manufactured above, fill with miso, then lay a parchment paper on it, and further put an oxygen scavenger, and then, at the upper end of the opening of the paper cup. A lid member was tightly adhered to the flange portion and the opening was sealed to produce a miso package. In the above-prepared miso package, generation of roasting pinholes, etc. was not observed, and further, excellent barrier properties against oxygen gas, water vapor, etc., and excellent aroma retention, and alteration of its contents was observed. In addition, it was excellent in laminate strength, endured distribution in the market, and excellent in storage and storage.

Example 5 (1). The barrier layer produced in the above Example 4 was used in the same manner, and a two-component curing type ester anchor coater was applied to the surface of the gas barrier coating film of the barrier layer in the same manner as in the above Example 4. Gravure coater (trade name, Takelac A3210 / Takenet A3075, coat amount: 1 g / m ² (dry state)) manufactured by Takeda Pharmaceutical Co., Ltd.
And then passed through a drying oven, and then the surface of the anchor-coating agent layer is subjected to ozone treatment while the extrusion temperature is 280 ° C.
, A low-density polyethylene resin [density, 0.919, melt index (MI), 9.0] was used, and this was extrusion-coated to form a low-density polyethylene resin layer having a thickness of 20 μm. . Next, the surface of the low-density polyethylene resin layer of the barrier layer produced above is opposed to one surface of the cup base paper having a basis weight of 300 g / m ² , and in-line corona treatment or ozone treatment is performed, and the layers are separated between the layers. Low density polyethylene resin [density, 0.923, melt index (MI), 3.7] is used, and this is extruded film thickness 2
While extruding to 0 μm, laminating both of them,
The above cup base paper and the barrier layer were laminated together. Further, a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm, which constitutes a barrier layer laminated with the above-mentioned cup base paper.
Two-component curing type ester-based anchor coating agent [Takeda Pharmaceutical Co., Ltd., trade name, Takelac A3210 / Takenet A3075, coating amount: 1 g /
m ² (dry state)] was applied with a gravure coater and passed through a drying oven, and then a low density polyethylene resin [density, 0.923, melt index] was applied to the surface of the anchor coating agent layer. (M.I), 3.7], which is extruded
To form a low-density polyethylene resin layer having a thickness of 20 μm. Further, after the corona treatment discharge treatment is applied to the other surface of the cup base paper laminated with the barrier layer as described above, the low-density polyethylene resin [density,
0.923, melt index (MI), 3.7]
Was used, and this was extrusion-coated to form a low-density polyethylene resin layer having a thickness of 20 μm. Next, on the surface of the low-density polyethylene resin layer having a thickness of 20 μm extruded on the surface of the biaxially stretched polyethylene terephthalate film having a thickness of 12 μm, which constitutes the barrier layer laminated with the above cup base paper, Low density polyethylene resin [Density, 0.923,
Melt index (MI) 3.7] and ethylene-α-olefin copolymer resin polymerized using a metallocene catalyst [density, 0.907, melt index (M.I.
I), 11.0], and two coextrusion laminated resin layers of a low density polyethylene resin layer and an ethylene-α-olefin copolymer resin layer polymerized using a metallocene catalyst. And the film thickness of the low-density polyethylene resin layer is 15 μm, and the film thickness of the ethylene-α / olefin copolymer resin layer polymerized by using a metallocene catalyst is 20 μm to form an innermost layer of 55 μm in total. Then, the laminated material according to the present invention was manufactured. (2). Then, using the laminated material produced above, a paper cup with a capacity of 500 cc according to the present invention was produced in the same manner as in Example 4 above, and was further used for miso packaging. Manufactured body. In the above-prepared miso package, generation of roasting pinholes, etc. was not observed, and further, excellent barrier properties against oxygen gas, water vapor, etc., and excellent aroma retention, and alteration of its contents was observed. In addition, it was excellent in laminate strength, endured distribution in the market, and excellent in storage and storage.

Comparative Example 1 In Example 1 above, instead of using the barrier layer produced in Example 1, the barrier film produced below was used, and otherwise the same as Example 1 above. Similarly, in the same manner as in Example 1, a paper cup having a capacity of 500 cc was manufactured, and the miso package was manufactured using the paper cup. (1). A biaxially stretched polyethylene terephthalate film having a thickness of 12 μm was used, and this film was attached to a delivery roll of a plasma enhanced chemical vapor deposition apparatus, and then the above biaxially stretched polyethylene terephthalate film was placed under the following conditions. A 200 Å-thick vapor-deposited film of silicon oxide was formed on the corona-treated surface of the glass film. (Deposition conditions) Deposition surface; Corona treatment surface Introduction gas amount; Hexamethyldisiloxane: Oxygen gas: Helium = 1.0: 3.0: 3.0 (unit: slm) Vacuum degree in vacuum chamber; 6 × 10 ⁻⁶ mBar Vacuum degree in vapor deposition chamber; 2 to 5 × 10 ⁻³ mBar Cooling / electrode drum power supply; 10 kW Line speed; 100 m / min Next, the above-mentioned 200 Å film thickness of silicon oxide vapor deposition film Immediately after the formation of the silicon oxide, a glow discharge plasma generator was used on the surface of the deposited film of silicon oxide, and the power was 9 kw, oxygen gas (O ₂ ): argon gas (Ar) = 7.0: 2.5 ( Unit: slm) is used, and mixed gas pressure is 6
× 10 ^-5 Torr, oxygen / at a processing speed of 420 m / min
Argon mixed gas plasma treatment was performed to form a plasma-treated surface in which the surface tension of the vapor-deposited film surface of silicon oxide was improved by 54 dyne / cm or more to form a barrier film.

Comparative Example 2 In the above Example 1, the barrier layer prepared in Example 1 was used in the same manner. First, the above Example 1 was applied to one side of a base paper for a cup having a basis weight of 300 g / m ^2. The surface of the gas barrier coating film of the barrier layer produced in 1. is made to face each other, and the interlayer is treated with a low density polyethylene resin [density, 0.923, melt index (MI), 3 .7] was used, and this was extrusion-laminated while being extruded with an extrusion film thickness of 20 μm to bond the above-mentioned cup base paper and the barrier layer. (That is, on the surface of the gas barrier coating film of the barrier layer produced in Example 1 above, a two-component curing type ester anchor coater was used.
The low density polyethylene resin layer having a thickness of 20 μm was not formed through the anchor coating layer of the coating agent. Then, except for the above, a paper cup having a capacity of 500 cc was produced in the same manner as in Example 1 and the miso package was produced using the same.

Experimental Example The paper cups produced in Examples 1 to 5 and Comparative Examples 1 to 2 above were measured for oxygen permeability, laminate strength, flavor of contents, and discoloration of contents. . (1). Measurement of Oxygen Permeability This is measured under the conditions of temperature 23 ° C and humidity 90% RH in the United States,
The measurement was performed using a measuring machine [model name, OXTRAN] manufactured by MOCON. (2). Measurement of Laminate Strength This is an interlayer laminar coating of a gas barrier coating film, which is prepared by preparing a measurement sample with a width of 15 mm under the conditions of room temperature, 23 ° C., humidity and 40% RH. The strength was measured by a measuring machine (manufactured by Orientec Co., Ltd., model name, Tensilon RTC-1310A). (3). Measurement of Flavor of Contents This is about a miso package, which was stored at room temperature (23 ° C.) for 60 days, opened, made miso soup, tasted by 5 panelists, and subjected to a sensory test. It was measured. (4). Measurement of the degree of discoloration This is the same as above, for the miso package, at room temperature (2
After being stored for 60 days, the miso was visually observed, and the degree of discoloration of the miso was measured and evaluated. The above test results are shown in Table 1 below.

[0086] In Table 1 above, the unit of oxygen permeability is [cc / m
² / day · 23 ° C./90% RH], the unit of laminate strength is [gf / 15 mm width], and the number in the flavor column indicates the number of people who have a good flavor.

As is clear from the test results shown in Table 1 above, the samples according to Examples 1 to 5 are excellent in oxygen permeability, laminate strength, etc., and suppress the generation of carbon dioxide gas. There was no discoloration and the flavor was good. On the other hand, those of Comparative Examples 1 and 2 are completely inferior in the laminating strength, cracks are generated in the vapor deposition film of the inorganic oxide, and the oxygen permeability is significantly lowered. Was also inferior, and as a result, the miso also discolored and the flavor was inferior.

[0088]

As is apparent from the above description, the present invention is based on at least the outermost layer, a paper base material, an adhesive layer composed of two polyolefin resin layers, and one surface of the base film having an inorganic oxide. A barrier layer consisting of a structure provided with a vapor deposition film of a material and a gas barrier coating film, and a laminated material is manufactured by sequentially laminating the innermost layer, or, for the above laminated material, excluding the outermost layer, At least a paper base material, an adhesive layer composed of two polyolefin resin layers, a barrier layer composed of a base film on which a vapor deposition film of an inorganic oxide and a gas barrier coating film are provided, , The innermost layer is sequentially laminated to produce a laminated material, and using the laminated material, first, a blank plate is punched into a desired shape, and further,
A blank plate is formed by processing an end surface treatment such as skiving and hemming, and then the blank plate is rolled into a tubular shape, and both end portions thereof are partially overlapped with each other, and a frame treatment is performed on the overlapping portion, or , Heat treatment such as hot air treatment,
The innermost layer, or the outermost layer and the innermost layer existing in the above-mentioned polymerized portion are heated and melted, and then pressed by a hot plate or the like to perform body sticking to form a body seal part, thereby forming a paper cup. A cylindrical cup body member is manufactured, on the other hand, the same laminated material as the above blank plate is used, and this is punched into a circular shape to manufacture a disk constituting the bottom portion, and then , The outer peripheral portion of the disk is erected into a cylindrical shape,
A bottom member having an upright forming portion is manufactured, and then the above-prepared bottom member is inserted into the above-mentioned tubular cup body member, and thereafter, the tubular cup body member and the bottom member are joined together. Of the innermost layer, or the outermost layer and the innermost layer existing in the joined portion by heating and melting the joined portion with hot air or the like, and then the tip portion of the tubular cup body portion with a curling mold. Bend inwardly, and cover the standing-up forming part constituting the above-mentioned bottom part, and the overlapping part of the leading end part of the above-mentioned tubular cup body member and the standing-up forming part of the bottom member is knurled from the inner diameter side. By knurling, the tubular cup body member and the bottom member are joined together to form a joint, and then the side opposite to the side where the bottom portion of the tubular cup body member is attached. Insert the tip end of the
The paper cup is manufactured by curling it outward while bending it with a mold for forming a top end flange portion to manufacture a paper cup. Then, the contents are filled from the opening at the top end into the paper cup manufactured above. Then, a lid member or the like is tightly adhered to the upper end flange portion of the paper cup to seal the opening, and a paper cup package in which the contents are filled and packaged is manufactured to form a silicon oxide forming a barrier layer. It also prevents the occurrence of cracks in the vapor deposition film of inorganic oxides such as aluminum oxide and enables low-temperature sealing to eliminate the occurrence of roasting pinholes, which allows the permeation of oxygen gas, water vapor, etc. It has an excellent barrier property to prevent the occurrence of seal failure due to the occurrence of pinholes.
It is possible to prevent a liquid leak and the like, prevent the deterioration of the contents, etc., and to manufacture a paper cup excellent in storability and storability.

[Brief description of drawings]

FIG. 1 is a schematic cross-sectional view showing a layer configuration of an example of a laminated material constituting a paper cup according to the present invention.

FIG. 2 is a schematic cross-sectional view showing a layer structure of an example of a laminated material forming a paper cup according to the present invention.

FIG. 3 is a schematic cross-sectional view showing a layer structure of an example of a laminated material forming the paper cup according to the present invention.

FIG. 4 is a schematic cross-sectional view showing a layer configuration of an example of a laminated material constituting a paper cup according to the present invention.

FIG. 5 is a schematic configuration diagram showing the configuration of the paper cup in each box making step of the paper cup according to the present invention using the laminated material shown in FIG. 1 above.

FIG. 6 is a schematic configuration diagram showing a configuration of the paper cup in each box-making step of the paper cup according to the present invention using the laminated material shown in FIG. 1 above.

FIG. 7 is a schematic configuration diagram showing a configuration of the paper cup in each box-making step of the paper cup according to the present invention using the laminated material shown in FIG. 1 above.

FIG. 8 is a schematic configuration diagram showing the configuration of the paper cup in each box-making step of the paper cup according to the present invention using the laminated material shown in FIG. 1 above.

FIG. 9 is a schematic configuration diagram showing an outline of a plasma enhanced chemical vapor deposition apparatus.

FIG. 10 is a schematic configuration diagram showing an outline of a roll-up type vacuum vapor deposition device.

FIG. 11 is a schematic configuration diagram showing a configuration of a conventional paper cup in each box making process.

[Explanation of symbols]

A, A ₁ , A ₂ , A ₃ Laminate 1 Outermost layer 2 Paper substrate 3 Polyolefin resin layer 4 Polyolefin resin layer 5 Adhesive layer 6 Base film 7 Inorganic oxide vapor deposition film 8 Gas barrier coating film 9 Barrier layer 10 Innermost layer

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 3E067 AA03 AA04 AB01 AB26 AB28                       AB81 AB96 BA07A BB01A                       BB09A BB11A BB14A BB18A                       BB25A BB26A BC03A BC07A                       CA05 CA06 CA24 CA30 EA04                       EA06 EA32 EE02 FA01 FC01                       GD02 GD06                 3E086 AA22 AB02 AC07 AD06 BA04                       BA13 BA14 BA15 BA24 BA33                       BB02 BB05 BB51 BB62 BB85                       CA01 CA11 CA12 CA13 CA28                       CA29 DA07 DA08                 4F100 AA01D AA19D AA20D AK01C                       AK03A AK21E AT00A BA05                       BA07 BA10A BA10E CB03                       DG10B EH23 EH46E EH66D                       GB16 JA13B JB20 JD02E                       JL12A

Claims (14)

[Claims] 1. A paper cup comprising a tubular cup body member and a bottom member for sealing the bottom of the tubular cup body member, wherein at least the tubular cup body member and the bottom member are An outer layer, a paper base material, an adhesive layer composed of two polyolefin resin layers, a barrier layer composed of a base film on which a vapor deposition film of an inorganic oxide and a gas barrier coating film are provided, A paper cup characterized by being made of a laminated material in which the innermost layers are sequentially laminated. 2. The laminated material is, except for the outermost layer, at least a paper base material, an adhesive layer consisting of two polyolefin resin layers, and a vapor deposition film of an inorganic oxide and a gas barrier on one surface of the base material film. The paper cup according to claim 1, wherein the paper cup is formed of a laminated material in which a barrier layer having a protective coating film and an innermost layer are sequentially laminated. 3. The laminated material comprises a laminated material in which a vapor deposition film of an inorganic oxide and a gas barrier coating film forming a barrier layer are laminated so as to face the surface of a paper base material. The paper cup according to any one of claims 1 to 2. 4. The paper cup according to any one of claims 1 to 3, wherein the outermost layer is a polyolefin resin layer having heat sealability. 5. The paper cup according to claim 1, wherein the paper base material is a paper base material having a basis weight of 80 to 600 g / m ² . 6. One of the two polyolefin-based resin layers forming the adhesive layer is formed on the vapor deposition film of inorganic oxide and the gas barrier coating film forming the barrier layer in advance. It is composed of a laminated polyolefin resin layer, the other polyolefin resin layer is characterized by comprising a melt-extruded resin layer melt-extruded and laminated between the paper substrate and one of the above polyolefin resin film layers. The paper cup according to any one of claims 1 to 5 above. 7. The paper cup according to claim 1, wherein the base film is a biaxially stretched resin film or sheet. 8. The vapor deposition film of an inorganic oxide comprises a vapor deposition film of an inorganic oxide by a chemical vapor deposition method or a physical vapor deposition method, according to claim 1. Paper cup described in. 9. The paper cup according to claim 1, wherein the vapor deposition film of inorganic oxide comprises a vapor deposition film of silicon oxide prepared by chemical vapor deposition. 10. The paper cup according to claim 1, wherein the vapor deposition film of the inorganic oxide is a vapor deposition film of aluminum oxide formed by physical vapor deposition. 11. The gas barrier coating film comprises at least:
Polyvinyl alcohol resin and the general formula R ¹ _m M (OR
² ) _n (In the formula, M represents a metal atom, R ¹ is the same or different and represents an organic group having 1 to 8 carbon atoms, R ² is the same or different, and is an alkyl group having 1 to 5 carbon atoms. Or an alkyl group having 1 to 6 carbon atoms or a phenyl group, m and n each represent an integer of 0 or more, and m + n represents the valency of M.), At least one selected from the group consisting of a hydrolyzate of an alcoholate, a condensate of the metal alcoholate, a chelate compound of the metal alcoholate, a hydrolyzate of the chelate compound and a metal acylate. The paper cup according to any one of claims 1 to 10, which comprises a gas barrier coating film of a gas barrier composition containing a seed. 12. The paper cup according to any one of claims 1 to 11, wherein the innermost layer is a polyolefin resin layer having a heat-sealing property. 13. The paper cup according to any one of claims 1 to 12, wherein the innermost layer is a coextruded laminated resin layer made of a polyolefin resin having heat sealability. 14. The innermost layer comprises a coextruded laminated resin layer of low-density polyethylene and an ethylene-α-olefin copolymer polymerized by using a metallocene catalyst, as described above. The paper cup according to any one of 1.