JP7380159B2 - barrier paper - Google Patents

Description

The present invention relates to a method for producing a paper material having a layer structure in which at least a paper base layer, an adhesive layer, and an inorganic vapor deposition layer are laminated adjacently in this order, and having barrier properties against oxygen gas and water vapor. .

In recent years, environmental problems caused by microplastics have been widely discussed, and in order to reduce the environmental impact of paper-based products, it is important to improve recyclability by making products as much as possible by using only paper. , there has been a demand for biodegradability to be taken into consideration.
Conventionally, packaging methods for suppressing the quality deterioration of the contents of foods, medical products, chemical products, cosmetics, etc. due to moisture and oxygen have included the use of packaging materials with high gas barrier properties, and the use of inert gas such as nitrogen gas to seal the content storage area. Gas is replaced with gas, and deoxidizers packaged with reduced iron powder are included in the package, but the performance is insufficient, the packaging cost increases, and the amount of waste increases. Problems have been raised, such as the fact that it only performs well in environments where there is water, and that it can be swallowed accidentally.
Packaging materials using paper have started to attract attention when considering the recycling and incineration of used packaging materials, but paper alone has insufficient gas barrier properties, so in order to improve gas barrier properties, If the surface of paper is coated with resin or laminated with metal foil or resin film with an inorganic vapor deposition layer, recycling and biodegradation of the paper material alone will be inhibited, and the resin component will burn and cause the incinerator to burn. This caused damage to the metal foil, and produced a large amount of incineration residue due to the metal foil.

Patent Document 1 discloses a laminate in which a gas barrier thin film layer formed by plasma polymerization is laminated on a base material made of paper or pulp mold that has a sealing layer made of a polycondensate of a polysaccharide and a silicon compound on its surface. has been done. However, in this laminate, it is necessary to increase the thickness of the sealing layer to about several tens of micrometers, and the method of coating and forming the sealing layer is limited. In addition, in order to insert a base material made of paper or pulp mold into the plasma polymerization apparatus when forming a thin film layer with gas barrier properties, the inside of the plasma polymerization apparatus is heated using paper powder or pulp powder generated from the paper or pulp mold. It is difficult to form a stable thin film layer with gas barrier properties, and the adhesion between the sealing layer and the thin film layer with gas barrier properties tends to be insufficient, resulting in poor gas barrier properties. It has the disadvantage of being easily unstable.

Patent No. 4622201

The object of the present invention is to provide a simple layer structure that includes at least a paper base layer, an adhesive layer, and an inorganic vapor deposition layer, has excellent barrier properties against oxygen gas and water vapor, has a high content of paper material, and is made of plastic material. An object of the present invention is to provide a barrier paper and a method for producing a barrier paper intermediate, which have a low content of metal elements and can be widely used even in applications where contents come into direct contact with each other.

In order to solve the above problems, the present inventors have developed a barrier paper and a barrier paper intermediate having a layer structure in which at least a paper base layer, an adhesive layer, and an inorganic vapor deposition layer are laminated adjacently in this order. It has been found that the manufacturing method can solve the above problems.
That is, the present invention is characterized by the following points.
1. A method for producing barrier paper having a layered structure in which at least a paper base layer, an adhesive layer, and an inorganic vapor deposition layer are laminated adjacently in this order,
A method for producing barrier paper, comprising at least the following steps 1 to 3,
Step 1) Forming an adhesive layer on the surface to be bonded of the paper base material to produce a paper base material with an adhesive layer,
Step 2) The paper base material with the adhesive layer obtained in Step 1 and the inorganic vapor deposited layer donor having an inorganic vapor deposited layer and an inorganic vapor deposited layer support layer are placed so that the adhesive layer and the inorganic vapor deposited layer face each other. a step of laminating the paper to produce a barrier paper intermediate;
Step 3) A step of peeling off the inorganic vapor deposited layer support layer from the barrier paper intermediate obtained in Step 2 to produce the barrier paper.
2. The inorganic vapor deposited layer contains one or more selected from the group consisting of aluminum, aluminum oxide, and silicon oxide.
The method for producing barrier paper as described in 1 above.
3. The thickness of the paper base layer is 5 μm or more and 200 μm or less,
The method for producing barrier paper according to 1 or 2 above.
4. The thickness of the adhesive layer is 1 μm or more and 20 μm or less,
The method for producing barrier paper according to any one of 1 to 3 above.
5. The thickness ratio occupied by the paper base layer in the barrier paper is 60% or more and less than 100%.
The method for producing barrier paper according to any one of 1 to 4 above.
6. The barrier paper has an oxygen permeability of 0.01 cc/m ² /24 hr/atm or more and 10 cc/m ² /24 hr/atm or less at 23° C. 90%,
The water vapor permeability at 40° C. 90% is 0.01 g/m ² /24 hr or more and 20 g/m ² /24 hr or less,
The method for producing barrier paper according to any one of 1 to 5 above.
7. The interlayer adhesion strength between the adhesive layer and the inorganic vapor deposition layer is in any one of classifications 0 to 3 in the cross-cut test of JIS K5600-5-6.
The method for producing barrier paper according to any one of 1 to 5 above.
8. The inorganic vapor deposited layer donor further has a release layer between the inorganic vapor deposited layer and the peelable inorganic vapor deposited layer support layer.
8. The method for producing barrier paper according to any one of 1 to 7 above.
9. The adhesive layer is a layer formed using a urethane resin composition,
The urethane resin composition contains a polyol and an isocyanate compound,
The polyol has two or more hydroxyl groups in one molecule, has a polyester structure part and/or a polyester polyurethane structure part in the main skeleton,
The polyhydric carboxylic acid derived structural part constituting the polyester structural part and/or the polyester polyurethane structural part contains an o-aromatic dicarboxylic acid derived structural part,
The isocyanate compound has two or more isocyanate groups in one molecule,
The method for producing barrier paper according to any one of 1 to 8 above.
10. A barrier paper produced by the barrier paper production method according to any one of 1 to 9 above. 11. A method for producing a barrier paper intermediate having a layer structure in which at least a paper base layer, an adhesive layer, an inorganic vapor deposited layer, and an inorganic vapor deposited layer support layer are laminated in contact with each other in this order, the method comprising:
A method for producing barrier paper, comprising at least the following steps 1 and 2,
Step 1) Forming an adhesive layer on a paper base material to produce a paper base material with an adhesive layer,
Step 2) An inorganic vapor-deposited layer donor having an inorganic vapor-deposited layer and an inorganic vapor-deposited layer support layer and the paper base material with an adhesive layer obtained in Step 1 are placed so that the inorganic vapor-deposited layer and the adhesive layer face each other. The process of laminating the paper to create a barrier paper intermediate.
12. The inorganic vapor deposited layer donor further has a release layer between the inorganic vapor deposited layer and the peelable inorganic vapor deposited layer support layer.
12. The method for producing a barrier paper intermediate according to 11 above.
13. The adhesive layer is a layer formed using a urethane resin composition,
The urethane resin composition contains a polyol and an isocyanate compound,
The polyol has two or more hydroxyl groups in one molecule, has a polyester structure part and/or a polyester polyurethane structure part in the main skeleton,
The polyhydric carboxylic acid derived structural part constituting the polyester structural part and/or the polyester polyurethane structural part contains an o-aromatic dicarboxylic acid derived structural part,
The isocyanate compound has two or more isocyanate groups in one molecule,
The method for producing a barrier paper intermediate according to 11 or 12 above.
14. A barrier paper intermediate produced by the method for producing a barrier paper intermediate according to any one of 11 to 13 above.

According to the manufacturing method of the present invention, it has a simple layer structure including a paper base layer, an adhesive layer, and an inorganic vapor deposition layer, has excellent barrier properties against oxygen gas and water vapor, has a high content of paper material, and is made of plastic. Barrier paper and barrier paper intermediates can be obtained that have a low content of materials and metal elements and can be used in a wide range of applications, even in applications where the contents come into direct contact.
Barrier paper has a layered structure in which a paper base layer, an adhesive layer, and an inorganic vapor-deposited layer are laminated adjacently in this order, making the layer structure simple and ecological. can be protected.
Further, by providing the adhesive layer between the paper base layer and the inorganic vapor deposited layer, even if the surface of the paper base layer is rough, the inorganic vapor deposited layer can be stably laminated.
Furthermore, since the content of paper material is high and the content of plastic materials and metal elements is low, recycling and biodegradation are facilitated, and the incinerator is not damaged and the incineration residue can be reduced.
That is, according to the present invention, while using a paper base material, an inorganic vapor deposition layer can be provided in the same way as when a resin base material is used, and a barrier paper that has the same gas barrier properties and is environmentally friendly can be obtained. can.
Furthermore, by forming the adhesive layer from a solvent-free adhesive or by forming the inorganic vapor deposition layer by transfer, it is environmentally friendly without generating a large amount of solvent vapor, and does not require large-scale vapor deposition equipment. Barrier paper can be produced ecologically using simple transfer equipment.

FIG. 1 is a cross-sectional view showing an example of the layer structure of the barrier paper of the present invention. FIG. 3 is a cross-sectional view showing an example of another embodiment of the layer structure of the barrier paper of the present invention. FIG. 3 is a cross-sectional view showing another example of the layer structure of the barrier paper of the present invention. FIG. 1 is a process diagram showing an example of the method for manufacturing barrier paper of the present invention. 1 is a schematic diagram showing an example of a barrier paper manufacturing apparatus of the present invention.

The present invention will be explained in more detail below. The explanation of the constituent elements described below is an example of the embodiment of the present invention, and the present invention is not limited to these contents unless the gist thereof is exceeded.
Note that in the present invention, the terms "film" and "sheet" have the same meaning.

<<Barrier paper intermediate and barrier paper manufacturing method>>
The method for producing a barrier paper intermediate of the present invention provides a barrier paper having a layer structure in which at least a paper base layer, an adhesive layer, an inorganic vapor deposited layer, and an inorganic vapor deposited layer support layer are laminated adjacently in this order. The present invention is a method for producing paper, and is a method for producing a barrier paper intermediate, which includes at least the following steps 1 and 2.
In addition to steps 1 and 2, the method for producing barrier paper may include other steps for forming other layers or processing the barrier paper intermediate.
The method for producing barrier paper of the present invention is a method for producing barrier paper having a layer structure in which at least a paper base layer, an adhesive layer, and an inorganic vapor deposition layer are laminated adjacently in this order, the method comprising: , is a method for producing barrier paper, including the following steps 1 to 3.
In addition to steps 1 to 3, the method for manufacturing barrier paper may include other steps for forming other layers or processing the barrier paper.

Step 1 is a step of forming an adhesive layer on at least one surface of the paper base material to be laminated or the surface of the inorganic vapor deposited layer of the inorganic vapor deposited layer donor.
The adhesive layer may be formed on either the paper base material or the inorganic vapor-deposited layer donor, or may be formed on both, or it may be provided between the paper base material and the inorganic vapor-deposited layer donor for bonding. Formation of the agent layer and adhesion may be performed simultaneously.
Prior to forming the adhesive layer, an anchor coat layer may be formed, and then a layer made of adhesive may be formed to improve the adhesion of the adhesive layer. The anchor coating agent is preferably formed by coating and drying.
The adhesive layer can be formed using a commonly known and publicly available general-purpose adhesive by a forming method depending on the type and characteristics of the adhesive.
Specific methods for forming the adhesive layer include, for example, forming a coating layer by applying a liquid adhesive composition, forming a dry laminate layer by a dry lamination method using a dry laminate adhesive, and non-solvent method. Examples include a non-solvent laminating method using an adhesive.
In the present invention, step 1 is not limited to the above specific example.
The paper base material may be a single sheet or a continuous sheet wound into a roll.

Step 2 is to use the paper base material with the adhesive layer or the inorganic vapor deposited layer donor obtained in Step 1 to laminate the paper base material and the inorganic vapor deposited layer donor via the formed adhesive layer. This is the step of producing a barrier paper intermediate.
Here, when laminating, the surface to be bonded of the paper base layer and the inorganic vapor deposited layer of the inorganic vapor deposited layer donor are stacked so as to face each other with an adhesive layer interposed therebetween, and the layer structure is as follows. A barrier paper intermediate having the following properties is obtained.
Layer structure: paper base layer/adhesive layer/inorganic vapor deposited layer/inorganic vapor deposited layer support material This can be done depending on the equipment, temperature, and pressure.
For example, when the adhesive layer is formed by a dry lamination method, first, in step 1, a dry laminating adhesive is applied to one side of the paper base material to be bonded and dried to form an adhesive layer. A paper substrate with an adhesive layer is obtained.
Then, in Step 2, the adhesive layer of the paper base material with an adhesive layer obtained in Step 1 and the inorganic vapor deposited layer of the inorganic vapor deposited layer donor are stacked facing each other, and then pressure is applied to bond and laminate. , a barrier paper intermediate is obtained. It can also be heated if necessary.
The pressurizing method and pressure during adhesion and lamination are preferably set so as not to damage the inorganic vapor deposited layer as much as possible. For example, it is preferable that the adhesive layer is softened by heating before lamination, and depending on the composition of the adhesive composition, the adhesive layer may be hardened by heating after lamination. The pressurizing pressure is preferably 0.1 MPa to 10 MPa.
In the present invention, steps 1 and 2 are not limited to the above specific examples.
The paper substrate and/or the inorganic deposited layer donor with the adhesive layer may be a single sheet or a continuous sheet wound into a roll.

Step 3 is a step of peeling off the inorganic vapor deposited layer support layer from the barrier paper intermediate obtained in Step 2 to produce a barrier paper having the following layer structure.
Layer structure: paper base layer/adhesive layer/inorganic vapor deposited layer The peeling can be performed using a general known and publicly available device and temperature depending on the type and characteristics of the adhesive layer and the method of forming the adhesive layer. can.
For example, when the barrier paper intermediate is a rolled continuous sheet, the inorganic vapor deposited layer support layer is continuously peeled off using a release roll, and each of the inorganic vapor deposited layer support layer and the barrier paper is rolled. You can take it.
In the present invention, step 3 is not limited to the above specific example.

[When forming an adhesive layer on a paper base material]
Each step in forming an adhesive layer on a paper base material is as follows.
Step 1) Forming an adhesive layer on the surface to be bonded of the paper base material to produce a paper base material with an adhesive layer,
Step 2) The paper base material with the adhesive layer obtained in Step 1 and the inorganic vapor deposited layer donor having an inorganic vapor deposited layer and an inorganic vapor deposited layer support layer are placed so that the adhesive layer and the inorganic vapor deposited layer face each other. a step of laminating the paper to produce a barrier paper intermediate;
Step 3) A step of peeling off the inorganic vapor deposited layer support layer from the barrier paper intermediate obtained in Step 2 to produce the barrier paper.

An example of a barrier paper intermediate and a method for manufacturing barrier paper is shown in FIG. 4.
First, in step 1, an adhesive layer 4 is formed on one side of the paper base layer 3.
Then, the 5 sides of the inorganic vapor deposited layer of the separately prepared inorganic vapor deposited layer transfer body 7 (layer structure: inorganic vapor deposited layer 5/inorganic vapor deposited layer support material 8) are stacked so as to face the adhesive layer 4. , to produce a barrier paper intermediate.
Next, the inorganic vapor deposited layer support material 8 is peeled off to obtain the barrier paper 1 (layer structure: inorganic vapor deposited layer 5/adhesive layer 4/paper base layer 3).

In this case, each step can be performed continuously as described below using, for example, a device such as the barrier paper manufacturing system (dry lamination type) 30 shown in FIG.
A continuous sheet of paper base material 31a is supplied from the paper base material unwinding section 31, an adhesive is coated on one surface in the adhesive coating section 32, and the solvent component of the adhesive is dried in the drying zone 33. Then, an adhesive layer is formed to produce an adhesive layer-attached paper base material 32a.
Then, separately, a continuous sheet of an inorganic vapor deposited layer transfer body 34a is supplied from an inorganic vapor deposited layer transfer body unwinding unit 34,
Using a rubber roll 35a and a metal roll 35b, the adhesive layer surface of the adhesive layer-coated paper base material 32a and the inorganic vapor deposited layer surface of the inorganic vapor deposited layer transfer body 34a are stacked so as to face each other, and the rubber roll 35a is stacked in the laminating section 35. and a metal roll 35b, and are pressed together to obtain a barrier paper intermediate 35c.
Here, the linear pressure between the rubber roll 35a and the metal roll 35b is preferably in the range of 0.1 MPa to 10 MPa.
Then, in the peeling section 36, the inorganic vapor deposited layer supporting material 38a of the barrier paper intermediate 35c is peeled off using release rolls 36a and 36b to obtain a continuous sheet of barrier paper 37a, which is wound on the barrier paper winding section 37. take. The inorganic vapor deposited layer supporting material 38a is wound up on the inorganic vapor deposited layer supporting material winding section 38. The release rolls 36a and 36b may be cooled or heated as necessary.

[When forming an adhesive layer on an inorganic vapor deposited layer donor]
Each step in forming an adhesive layer on an inorganic vapor-deposited layer donor is as follows.
Step 1) forming an adhesive layer on the inorganic vapor deposited layer surface of the inorganic vapor deposited layer donor having an inorganic vapor deposited layer and an inorganic vapor deposited layer support layer to produce an inorganic vapor deposited layer donor with an adhesive layer;
Step 2) The adhesive layer-attached inorganic vapor deposited layer donor obtained in Step 1 and a paper base material are laminated so that the adhesive layer and the inorganic vapor deposited layer face each other to produce a barrier paper intermediate. The process of
Step 3) A step of peeling off the inorganic vapor deposited layer support layer from the barrier paper intermediate obtained in Step 2 to produce the barrier paper.

<<Barrier paper>>
The barrier paper of the present invention is a barrier paper having a layer structure in which at least a paper base layer, an adhesive layer, and an inorganic vapor deposition layer are laminated adjacently in this order, as shown in FIG. .
When a gas barrier packaging material made from barrier paper forms a package, the paper base layer may be located on the inside or outside, and there is no particular limitation.

The barrier paper can further include layers having various functions, if necessary.
For example, a surface protective layer for protecting the inorganic vapor deposited layer may be included on the outer surface of the inorganic vapor deposited layer, a printing layer may be included on the surface of the paper base material layer opposite to the inorganic vapor deposited layer, and the deformation resistant layer may be included. A reinforcing layer may be included to satisfy various conditions such as durability, drop impact resistance, pinhole resistance, heat resistance, sealability, quality maintenance, workability, hygiene, and others.
It can also have a functional layer for improving gas barrier properties, imparting aroma retention to the contents to be filled and packaged, and preventing the contents from producing off-taste, off-odor, etc.
Furthermore, a general-purpose adhesive layer can be included between each of the above layers or within each layer to improve interlayer adhesion.
Barrier paper having the above-mentioned layer structure can be widely used even in applications where the contents come into direct contact with each other.

The thickness ratio occupied by the paper base layer in the barrier paper is preferably 60% or more and less than 100%, more preferably 70% or more and 99.9% or less, and more preferably 80% or more and 99% or less. If it is lower than the above range, the efficiency of recyclability and biodegradability of the paper base material tends to decrease, and even if it is higher than the above range, the efficiency of recyclability and biodegradability will not change further and will be insufficient. There is a risk that the barrier properties may not be exhibited.

The gas barrier property of the barrier paper is preferably such that the oxygen permeability measured according to the JIS K7126 method at 23° C. 90% is 0.01 cc/m ² /24 hr/atm or more and 10 cc/m ² /24 hr/atm or less, More preferably, it is 0.01 cc/m ² /24 hr/atm or more and 5 cc/m ² /24 hr/atm or less. It is difficult to make the oxygen permeability smaller than the above numerical range, and when it is larger than the above numerical range, it is difficult to sufficiently suppress the permeation of oxygen and suppress the deterioration of the contents.
The water vapor permeability measured in accordance with the JIS K7129 method at 40°C 90% is preferably 0.01 g/m ² /24 hr or more and 20 g/m ² /24 hr or less, and 0.01 g/m ² /24 hr or more. , more preferably 10 g/m ² /24 hr or less. It is difficult to make the water vapor permeability smaller than the above numerical range, and if it is larger than the above numerical range, it is difficult to sufficiently suppress the permeation of water vapor and suppress the deterioration of the contents.

The barrier paper of the present invention can be provided with surface functions such as chemical functions, electrical functions, magnetic functions, mechanical functions, frictional/abrasion/lubrication functions, optical functions, thermal functions, and biocompatibility. It is also possible to perform secondary processing for this purpose.
Examples of secondary processing include embossing, painting, adhesion, printing, metallization (plating, etc.), machining, surface treatment (antistatic treatment, corona discharge treatment, plasma treatment, photochromism treatment, physical vapor deposition, chemical vapor deposition, coating, etc.). Further, the laminate of the present invention can also be subjected to lamination processing (dry lamination or extrusion lamination), bag making processing, and other post-processing processing.

When laminating the layers constituting the barrier paper, if necessary, the surface of each layer can be pretreated with a pretreatment such as corona treatment or ozone treatment. In addition, for example, anchor coating agents such as isocyanate-based (urethane-based), polyethyleneimine-based, polybutadiene-based, organic titanium-based, etc., or polyurethane-based, polyacrylic-based, polyester-based, epoxy-based, polyvinyl acetate-based, cellulose-based, etc. Anchor coating agents such as laminating adhesives such as , etc. can be optionally used.

[Contents]
In the above, the contents include coffee beans, tea leaves, cheese, snacks, rice crackers, fresh and semi-fresh sweets, fruits, nuts, vegetables, fruits, fish and meat products, paste products, dried fish, smoked foods, tsukudani, raw rice, Foods such as rice, rice cakes, infant foods, jams, mayonnaise, ketchup, edible oil, dressings, sauces, spices, dairy products, pet food, and beverages such as beer, wine, fruit juice, green tea, coffee, etc. Examples include, but are not limited to, pharmaceuticals, cosmetics, shampoos and conditioners, detergents, metal parts, and electronic parts.

≪Paper base layer≫
If the paper base layer has strength, toughness, heat resistance, and other mechanical, physical, and chemical properties that can sufficiently withstand general adhesive layer forming processes and lamination processes, General known and publicly used paper base materials can be used, and there are no particular limitations.
Paper substrates include, for example, bleached or unbleached paper substrates with strong size, pure white roll paper, kraft paper, paperboard, coated paper, cast coated paper, milk base paper, processed base paper, fine paper, fine paper, etc. Coated printing paper, coated printing paper, resin-coated paper, release base paper, double-sided coated release base paper, etc. can be used, and paper base materials on which an intermediate layer such as a sealing layer or a resin layer has been formed in advance can be used. There may be.
Further, the paper base material layer may be composed of one layer, or may be composed of two or more layers made of the same or different paper base materials. The paper base materials can be laminated by any laminating means via an adhesive layer.
A wide variety of paper substrates can be used in the present invention. Specific examples are given below.

Generally, the surface of paper base material is porous and uneven, so when forming an inorganic vapor deposited layer on paper base material, a sealing coat with a thickness of about 20 μm or more is applied to the paper base material surface. However, in the present invention, such a thick sealing coat is not necessary because the inorganic vapor-deposited layer is laminated on the paper base material via the adhesive layer.
Generally, when a paper base material is placed in a vapor deposition apparatus and an inorganic vapor deposition layer is formed under reduced pressure, the pressure inside the vapor deposition apparatus is reduced to an atmospheric pressure suitable for vapor deposition by paper powder generated from the paper base material. As a result, it is difficult to form a stable inorganic vapor deposited layer, which tends to cause insufficient adhesion between the formed inorganic vapor deposited layer and the paper base material, and the gas barrier properties tend to become unstable. In the present invention, since the inorganic vapor-deposited layer is laminated on the paper base material via the adhesive layer, the inorganic vapor-deposited layer and the paper base material can be bonded together without placing the paper base material in a vapor deposition apparatus and performing vapor deposition. It is possible to laminate.

The basis weight and/or thickness of the paper base layer can be set appropriately by those skilled in the art, but for the purpose of imparting appropriate strength and stiffness to the laminate, the basis weight is approximately 30 g/m ² to 600 g/m. ^{The second} place is preferable, and the one with a basis weight of about 50 g/m ² to 450 g/m ² is more preferable. Further, the thickness of the paper base layer is preferably 5 μm to 200 μm, more preferably 30 μm to 100 μm, and even more preferably 40 to 80 μm.
If the basis weight and/or thickness is smaller than the above range, curling and waving will easily occur during the production of barrier paper, while if it is larger than the above range, the rigidity will be too strong and workability will be poor, and the winding diameter will be reduced. becomes large, and work efficiency tends to decrease.

The raw material pulp for the paper base material is preferably a mixture of softwood pulp (N material) and hardwood pulp (L material). This makes it easy to obtain strength and smoothness that can withstand the release paper manufacturing process and the transfer product manufacturing process. Further, the mixing ratio of hardwood pulp (L material) is preferably 50% to 90%. This further improves smoothness.
Further, in order for the paper base material to have sufficient heat resistance, neutral paper is preferable, and neutral paper sized using an alkyl ketene dimer as a sizing agent is more preferable.

If it is necessary to improve the surface smoothness or hardness of the paper base material, a smoothing layer made of clay and/or polyolefin resin can be provided on the surface of the paper base material.
When using a material with a relatively rough surface, such as kraft paper or high-quality paper, as a paper base material, it is easy to improve the surface smoothness of the paper base material by providing a smoothing layer containing a polyolefin resin. .

As the clay, any clay commonly referred to as clay can be used without particular limitation. As the clay, for example, kaolin, talc, bentonite, smectite, vermiculite, mica, chlorite, kibushi clay, gyrome clay, halloysite, mica, etc. can be used. As clay, talc has low hardness (Mohs hardness: 1) and excellent heat resistance, so it can improve heat resistance and dimensional stability during embossing.
The clay preferably contains calcium carbonate, titanium dioxide, amorphous silica, foamable barium sulfate, satin white, etc. as pigments. By using calcium carbonate or titanium dioxide as a pigment, the surface smoothness of the clay coat layer can be increased. Furthermore, since calcium carbonate is inexpensive, it is preferably used.

A coating liquid for applying a smoothing layer containing clay contains the above-mentioned clay in a solvent, a binder, and other pigments and additives as necessary. As the solvent, water, alcohol, etc. are usually used. The binder is usually a latex binder (e.g. styrene-butadiene latex, acrylic latex, vinyl acetate latex), a water-soluble binder (e.g. starch (modified starch, oxidized starch, hydroxyethyl etherified starch, phosphate ester) starch), polyvinyl alcohol, casein, etc.) are used. As additives, pigment dispersants, antifoaming agents, antifoaming agents, viscosity modifiers, lubricants, waterproofing agents, water retention agents, etc. are used.
The method for applying the clay-containing coating liquid is not particularly limited, but air knife coating, blade coating, short dwell coating, cast coating, and the like may be used.

The thickness of the smoothing layer containing clay is not particularly limited, but the basis weight after drying is usually 5 g/m ² to 40 g/m ² , preferably 10 g/m ² to 40 g/m ² . If the basis weight after drying is smaller than the above range, the smoothness tends to be poor, and if it is larger than the above range, the smoothing layer made of clay is likely to cause cohesive failure, and there is a risk that the adhesion will be likely to decrease. Moreover, it is inferior in terms of cost performance.
The smoothing layer made of polyolefin resin may be formed by extrusion coating on the base layer.
The thickness of the smoothing layer is not particularly limited, but is preferably 10 μm to 60 μm.

In addition, the paper base material has processability, heat resistance, weather resistance, mechanical properties, dimensional stability, antioxidant properties, slipperiness, mold release properties, flame retardance, mold resistance, electrical properties, etc. Plastic compounding agents and additives such as lubricants, crosslinking agents, antioxidants, ultraviolet absorbers, light stabilizers, fillers, reinforcing agents, antistatic agents, and pigments for the purpose of improving and modifying physical properties, strength, etc. etc., and the amount of addition can be arbitrarily determined depending on the purpose within a range that does not adversely affect other performances.

In order to improve the adhesion between the paper base material and/or the base material layer and other layers, a paper base material having a coating layer containing a resin etc. on the surface may be used as necessary, or a paper base material and/or a paper base material layer may be used. Alternatively, physical surface treatments such as corona discharge treatment, ozone treatment, plasma treatment, glow discharge treatment, sandblasting treatment, etc., or oxidation treatment using chemicals may be applied to the surface of the paper base layer that comes into contact with the adhesive. A chemical surface treatment can also be applied in advance.

≪Adhesive layer≫
The adhesive layer can be formed using a commonly known and publicly used general-purpose adhesive, and the layer made of the adhesive may be formed after forming the anchor coat layer in advance.
Further, since the adhesive layer is adjacent to the inorganic vapor deposited layer, the effect of protecting the inorganic vapor deposited layer can be imparted by using an adhesive having a specific composition.

The adhesive may be solvent-based, water-based, or solvent-free, but the amount of residual solvent in the adhesive layer is preferably small, preferably 6 mg/m ² or less. . The amount of residual solvent is most preferably 0 mg/m ² , but substantially preferably 6 mg/m ² or less.
By keeping the amount of residual solvent in the adhesive layer within the above range, it is advantageous in suppressing a decrease in adhesive strength due to residual solvent, and it also prevents distortion and minute peeling defects at the interface with the inorganic vapor deposited layer due to volumetric shrinkage during drying. This is advantageous in that it suppresses the generation of gas and suppresses deterioration of gas barrier properties. Furthermore, it is advantageous in that it suppresses the generation of solvent odor from the barrier paper.
In order to reduce the amount of residual solvent, it is advantageous and preferable to form the adhesive layer using a solvent-free or water-based adhesive.

However, if there is sufficient interlayer adhesion, the formed adhesive layer can withstand use even if the amount of residual solvent is more than 6mg/ ^m2 , and depending on the usage conditions, the odor of the solvent can be removed by other methods. The above requirements do not necessarily have to be met, as the problem can be solved using a method.
Here, if the barrier paper does not contain a structure containing a solvent other than the adhesive layer, the solvent content of the adhesive layer can be detected by measuring the solvent content of the entire barrier paper. can.
In addition, in the present invention, "solvent-free" means that it does not actively contain a solvent, and the adhesive is a material that contains a trace amount of solvent derived from the solvent remaining in the raw material. The content may be within a range that can reduce the amount of residual solvent in the solvent to 6 mg/m ² or less.

[solvent]
The solvent contained in the solvent-based adhesive dissolves the resin raw material that makes up the solvent-based adhesive, has an appropriate boiling point and volatility for the barrier paper manufacturing process, and has a suitable boiling point and volatility for the formed adhesive layer. It is preferable that the solvent content can be reduced to 6 mg/m ² or less.
When a highly polar solvent is used, workability tends to be poor. For example, when using a highly soluble solvent such as acetone, it has a low boiling point and easily absorbs water from the outside air, so the viscosity of the crack-resistant adhesive tends to increase due to the reaction between water and isocyanate. may occur.

[General-purpose adhesive]
The general-purpose adhesive layer may be, for example, a non-solvent laminating method using an adhesive composition non-solvent adhesive, or a layer formed by dry lamination using a dry laminating adhesive (dry lamination layer). good.

Examples of the resin contained in the above adhesive composition include two-part curable urethane adhesive, polyester polyurethane adhesive, polyether polyurethane adhesive, acrylic adhesive, polyester adhesive, and polyamide adhesive. Adhesives, polyvinyl acetate adhesives, epoxy adhesives, rubber adhesives, polyolefin resins, and polyolefin resins may be mixed with acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, etc. Acid-modified polyolefin resins, polyvinyl acetate resins, poly(meth)acrylic resins, polyvinyl chloride resins, etc. that are acid-modified by graft polymerization or copolymerization using saturated carboxylic acids or their anhydrides, etc. Resin can be used. These resins can be used alone or in combination.

The adhesive layer may contain additives such as antioxidants, ultraviolet absorbers, light stabilizers, antistatic agents, anti-blocking agents, flame retardants, cross-linking agents, colorants, etc., to the extent that the characteristics of the present invention are not impaired. can be included.
The thickness of the adhesive layer is not particularly limited, but is preferably 1 g/m ² or more and 20 g/m ² or less, more preferably 2 g/m ² or more and 10 g/m ² or less, or 1 μm or more, The thickness is preferably 20 μm or less, more preferably 2 μm or more and 10 μm or less. If it is thinner than the above numerical range, it tends to be difficult to exhibit sufficiently high and stable adhesiveness, and if it is thicker than the above numerical range, the adhesiveness does not change much and the forming method tends to be limited, which is not preferable.

[Adhesive that protects the inorganic vapor deposited layer]
The adhesive that protects the inorganic vapor deposited layer is an adhesive that can maintain the gas barrier properties of the barrier paper by protecting the inorganic vapor deposited layer that exhibits gas barrier properties, even if the adhesive itself does not have gas barrier properties. .
For example, when a bending load is applied to the barrier paper, it suppresses the occurrence of cracks in the inorganic vapor-deposited layer, and even when minute cracks begin to form in the inorganic vapor-deposited layer after the bending load, it suppresses the deterioration of gas barrier properties. It is an adhesive that can be used.
As the adhesive for protecting the inorganic vapor deposited layer, a urethane resin composition is preferable, and the urethane resin composition contains a specific polyol having two or more hydroxyl groups in one molecule and two isocyanate groups in one molecule. It is preferable to contain at least one specific isocyanate compound.
Moreover, the adhesive that protects the inorganic vapor deposition layer may further contain a phosphoric acid compound. It may also contain an inorganic compound.

Further, the adhesive for protecting the inorganic vapor deposited layer may be a solvent-free adhesive or a solvent-based adhesive.
Here, in the present invention, "solvent-free" means that it does not actively contain a solvent, and the adhesive that protects the inorganic vapor-deposited layer contains a trace amount of solvent derived from the solvent remaining in the raw material. The residual solvent may be contained within a range that can reduce the amount of residual solvent in the adhesive layer, for example, 6 mg/m ² or less.
By setting the amount of residual solvent in the adhesive layer consisting of an adhesive that protects the inorganic vapor-deposited layer within the above range, it is advantageous in terms of suppressing the decrease in adhesive strength between the layers of the laminate due to residual solvent, and it is advantageous in terms of suppressing the decrease in adhesive strength between the layers of the laminate due to residual solvent and reducing volume shrinkage during drying. This is advantageous in that it suppresses the occurrence of distortion and minute peeling defects at the interface with the inorganic vapor deposited layer, thereby suppressing deterioration of gas barrier properties. Furthermore, in a package made from a packaging material using the obtained laminate, it is advantageous in that the contents are prevented from having a solvent odor.
However, as long as there is sufficient interlayer adhesion, there is no problem as long as the amount of residual solvent in the formed adhesive layer is more than 6 mg/ ^m2 , for example, as long as it can withstand use. Solvent odor can be resolved in other ways.
In the case of a solvent-free type, it is preferable because it is easy to suppress the amount of residual solvent in the formed adhesive layer, for example, within the above range, and since less solvent is used and released, there is less burden on the environment. can be reduced.
The solvent-free adhesive that protects the inorganic vapor deposited layer is used during lamination, for example, by heating to lower the viscosity without using a solvent.For example, the adhesive layer is formed by a non-solvent laminating method or a roll coating method. can do.
In the case of a solvent-based adhesive, it is preferable to dry the adhesive layer sufficiently so that the amount of residual solvent in the formed adhesive layer is reduced, for example, within the above range.
The adhesive that protects the solvent-based inorganic vapor-deposited layer can be applied to at least one of the adhesive surfaces, dried, and then laminated by forming an adhesive layer using a dry lamination method in which the adhesive surfaces are opposed to each other and bonded. preferable.

When an adhesive is used to protect the inorganic vapor deposited layer, the glass transition temperature of the adhesive layer is preferably in the range of -30°C to 80°C, more preferably 0°C to 70°C, and even more preferably 25°C. ~70°C. If it is higher than the above range, the flexibility near room temperature will be weak, and the adhesion to adjacent layers may be poor, leading to a decrease in adhesion. If it is lower than the above range, there is a risk of a decrease in adhesion due to insufficient cohesive force.
Commercially available adhesives for protecting such inorganic vapor deposited layers include the solvent-based barrier adhesive Paslim (base resin VM001/curing agent 108CP) manufactured by DIC Corporation, and the solvent-free barrier adhesive Paslim. (Main agent NSRD011/Curing agent NSRD006) and the like are known.

The adhesive layer using an adhesive that protects the inorganic vapor deposition layer tends to have a higher protective effect when it is thicker, but it is preferably 1.5 μm or more and 20 μm or less. If it is thinner than the above range, the protective effect tends to be insufficient, and if it is thicker than the above range, the rigidity of the adhesive layer itself becomes too strong, which tends to lead to a decrease in the protective effect.

(Specific polyol having two or more hydroxyl groups in one molecule)
Polyols having two or more hydroxyl groups in one molecule include two or more hydroxyl groups in one molecule, and the main skeleton is a polyester structure part, a polyester polyurethane structure part, a polyether structure part, and a polyether polyurethane structure part. Those having one or more selected from the group are preferred, and those having a polyester structure in the main skeleton are particularly preferred.
Most preferably, the polyester structure includes a polyester structure formed from an o-aromatic dicarboxylic acid and an aliphatic diol.
The polyester structure can be obtained, for example, by subjecting polyhydric carboxylic acids and polyhydric alcohols to a polycondensation reaction by a known and commonly used method, but the synthesis method is not limited thereto.
It is preferable that 70 to 100% by mass of the polyhydric carboxylic acid derived structural parts in the polyester structural part or the polyester polyurethane structural part be o-aromatic dicarboxylic acid derived structural parts. Here, o-aromatic dicarboxylic acids refer to o-aromatic dicarboxylic acids and their anhydrides and ester-forming derivatives.

Polyvalent carboxylic acids refer to polyvalent carboxylic acids and their anhydrides and ester-forming derivatives, and include, for example, aliphatic polyvalent carboxylic acids and aromatic polyvalent carboxylic acids.
Specific examples of aliphatic polycarboxylic acids include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid.
Specific aromatic polycarboxylic acids include o-phthalic acid, terephthalic acid, isophthalic acid, pyromellitic acid, trimellitic acid, 1,2-naphthalene dicarboxylic acid, 1,8-naphthalene dicarboxylic acid, 2,3 -Naphthalene dicarboxylic acid, 1,4-naphthalene dicarboxylic acid, 2,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, naphthalic acid, biphenyl dicarboxylic acid, 1,2-bis(phenoxy)ethane-p,p' - dicarboxylic acids and anhydrides or ester-forming derivatives of these dicarboxylic acids; polybasic acids such as p-hydroxybenzoic acid, p-(2-hydroxyethoxy)benzoic acid, and ester-forming derivatives of these dihydroxycarboxylic acids; Can be mentioned.
Specific o-aromatic dicarboxylic acids include o-phthalic acid, 1,2-naphthalene dicarboxylic acid, 1,8-naphthalene dicarboxylic acid, 2,3-naphthalene dicarboxylic acid, and anhydrides or esters of these dicarboxylic acids. Formative derivatives and the like can be mentioned.
In the present invention, the above polyhydric carboxylic acids may be used alone or in combination of two or more.

Examples of polyhydric alcohols include aliphatic polyhydric alcohols and aromatic polyhydric phenols.
Specifically, the aliphatic polyhydric alcohols include ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, cyclohexanedimethanol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1, Examples include 6-hexanediol, methylpentanediol, dimethylbutanediol, butylethylpropanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, and tripropylene glycol.
Specific examples of aromatic polyhydric phenols include hydroquinone, resorcinol, catechol, naphthalene diol, biphenol, bisphenol A, hisphenol F, tetramethylbiphenol, ethylene oxide extension products, and hydrogenated alicyclic compounds. etc. can be exemplified.
In the present invention, the above polyhydric alcohols may be used alone, or two or more types may be used in combination.

(Specific isocyanate compound having two or more isocyanate groups in one molecule)
The isocyanate compound having two or more isocyanate groups in one molecule may be either aromatic or aliphatic, and may be either a low-molecular compound or a high-molecular compound, as long as it has two or more isocyanate groups in the molecule. good. For example, known compounds such as diisocyanate compounds having two isocyanate groups and polyisocyanate compounds having three or more isocyanate groups can be used. Alternatively, a blocked isocyanate compound obtained by an addition reaction using a known isocyanate blocking agent by a known and commonly used method can also be used.
Among the above isocyanate compounds, those containing an aromatic ring structure and/or a polyurethane structure containing an aromatic ring in the main skeleton are preferable.
From the viewpoint of adhesive properties, polyisocyanate compounds are preferred, and from the viewpoint of gas barrier properties, those having an aromatic ring are preferred. In particular, isocyanate compounds containing a meta-xylene skeleton are preferred because they are expected to improve gas barrier properties not only through hydrogen bonding between urethane groups but also through π-π stacking between aromatic rings.

Specific compounds include, for example, tetramethylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, metaxylylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, or trimers of these isocyanate compounds. , and an excess of these isocyanate compounds, such as ethylene glycol, propylene glycol, metaxylylene alcohol, 1,3-bishydroxyethylbenzene, 1,4-bishydroxyethylbenzene, trimethylolpropane, glycerol, pentaerythritol, erythritol, Low-molecular active hydrogen compounds such as sorbitol, ethylenediamine, monoethanolamine, diethanolamine, triethanolamine, metaxylylene diamine, and their alkylene oxide adducts, and high-molecular active hydrogen compounds such as various polyester resins, polyether polyols, and polyamides. Examples include adducts, burettes, allophanates, etc. obtained by reacting with the like.

≪Inorganic vapor deposited layer≫
The inorganic vapor deposited layer is a layer made of a vapor deposited inorganic compound, and there is no particular limitation on the inorganic vapor deposited layer support material on which the inorganic vapor deposited layer is formed by vapor deposition.
For example, the inorganic vapor deposited layer may be an inorganic vapor deposited layer directly formed by vapor deposition on the adhesive layer of the paper base material layer on which the adhesive layer is formed (directly formed inorganic vapor deposited layer).
Alternatively, once an inorganic vapor deposited layer transfer body is produced by vapor deposition on another inorganic vapor deposited layer support material,
It may be an inorganic vapor deposited layer (transferred inorganic vapor deposited layer) laminated by transfer from the inorganic vapor deposited layer transfer body to a paper base layer via an adhesive layer. Here, the adhesive layer may be formed on the paper base layer, or may be formed on the inorganic vapor deposited layer of the inorganic vapor deposited layer transfer body.
The inorganic vapor deposited layer laminated by transfer has less contamination, has higher interfacial adhesion with the adhesive layer, is homogeneous and stable, and has gas barrier properties than the inorganic vapor deposited layer that is formed directly on the paper base layer. be able to excel in
It is preferable that the interlayer adhesion strength between the adhesive layer and the inorganic vapor deposited layer be in any of the classifications 0 to 3 in a cross-cut test according to JIS K5600-5-6. When the barrier paper is classified as 4 or 5, which is lower than the above range, peeling occurs when the barrier paper is used, and gas barrier properties tend to deteriorate.

A summary of the evaluation of the interlayer adhesion strength for the inorganic vapor deposited layer is as follows.
The inorganic vapor deposited layer on the barrier paper is cut through the inorganic vapor deposited layer with a cutter knife or the like to form a plurality of right-angled lattice patterns. At this time, it is preferable to use a cross-cutting jig that can form a plurality of right-angled lattice patterns continuously and neatly.
Next, an adhesive tape having an adhesive layer on one side, such as adhesive cellophane tape, is attached so as to cover the entire grid formed above.
Then, using Tensilon, the attached adhesive tape is peeled off from the edge, and the degree of peeling of the inorganic vapor deposited layer is visually observed, and the results are classified according to the following evaluation criteria.
Here, the size of one side of the lattice pattern is preferably 1 to 5 mm, more preferably 1.5 to 3 mm, and even more preferably about 2 mm.
The number of lattice patterns is preferably 15 to 50, more preferably 20 to 30, and even more preferably about 25.
The width and length of the adhesive tape is preferably such that it can cover all of the formed lattice pattern and is easy to peel off.
The adhesive tape is preferably peeled off using a Tensilon or the like at a constant speed of preferably 1 to 5 mm/min, more preferably 2 to 4 mm/min, and even more preferably about 3 mm/min.

Category 0: The edges of the cut are completely smooth and there is no peeling on any grid.
Category 1: There is small peeling of the paint film at the intersection of cuts. However, the cross-cut portion is clearly affected by no more than 5%.
Category 2: Peeling of the coating along the cut edges and/or at intersections. The cross-cut area clearly affects between 5% and 15%.
Category 3: The paint film is partially or completely peeled off along the edges of the cut, and/or various parts of the eye are partially or completely peeled off. The cross-cut area is affected by more than 15% and less than 35%.
Category 4: The paint film has partially or completely peeled off along the edge of the cut, and/or some spots have partially or completely peeled off. The cross-cut area is affected within a range that clearly does not exceed 35%.
Category 5: Any level of peeling that cannot be classified even in Category 4.

The inorganic vapor-deposited layer is a layer that suppresses the permeation of gases such as oxygen gas and water vapor, but if the inorganic vapor-deposited layer is opaque, it has a light-shielding property against sunlight, etc., and may also have aroma-retaining properties for the contents. can.
Examples of the inorganic compound constituting the inorganic vapor deposition layer include metals, metal oxides, metal nitrides, metal carbides, and the like.
Specific examples of the metal elements constituting the above-mentioned inorganic compounds include aluminum (Al), silicon (Si), magnesium (Mg), calcium (Ca), potassium (K), tin (Sn), sodium (Na ), boron (B), titanium (Ti), lead (Pb), zirconium (Zr), yttrium (Y), zinc (Zn), vanadium (V), barium (B
a), chromium (Cr), and the like.

As specific examples of inorganic compounds, metals made of the above-mentioned metal elements, metal oxides, metal nitrides, metal carbides, etc. are preferable, and in addition to these, indium tin oxide (ITO), indium tin oxide (ITO), etc. Composite _inorganic compounds such as _SiO
Among the above, aluminum, aluminum oxide, and silicon oxide are preferred.

The average composition of an inorganic compound is expressed as MO _x , MO _x C _y , such as SiO _x , AlO _x , SiO _x C _y (wherein, M represents a metal element, and the values of x and y The range varies depending on the metal element.) In the case of metal oxides, the value of X ranges from 0 to 2 for silicon, 0 to 1.5 for aluminum, 0 to 1 for magnesium, 0 to 1 for calcium, and 0 to 0. for potassium. 5. Tin: 0-2, sodium: 0-0.5, boron: 0-1, 5, titanium: 0-2, lead: 0-1, zirconium: 0-2, yttrium: It can take values in the range 0 to 1.5.
In the above MO _x , when x=0, it is metal and not transparent, and the upper limit of the range of x is the value when completely oxidized.

In the present invention, it is preferable to use aluminum oxide with x in the range of 0.5 to 1.5, and silicon oxide with x in the range of 1.0 to 2.0.
The inorganic vapor deposition layer may be formed of one type of these inorganic compounds, or may be used in combination of two or more types, or may be used as a mixture of two or more types. Further, it may be composed of a single layer, or may be composed of multiple layers having the same or different compositions.
When the inorganic vapor-deposited layer is multilayer, each layer can be vapor-deposited to have high gas barrier properties, so it is possible to obtain even higher gas barrier properties than that of a single layer, and furthermore, the composition of the inorganic vapor-deposited layer If they are different, the inorganic vapor deposited layers are different discontinuous layers, so that permeation of oxygen gas, water vapor, etc. can be suppressed more efficiently.

In order to obtain sufficient oxygen barrier properties and water vapor barrier properties, the thickness of the inorganic vapor deposited layer is preferably 30 Å to 3000 Å, more preferably 40 Å to 2500 Å, and even more preferably 50 Å to 2000 Å.
More specifically, in the above PVD method, the thickness of the inorganic vapor deposited layer made of aluminum oxide is preferably about 30 Å to 1000 Å, more preferably about 50 Å to 500 Å.
Furthermore, in the above CVD method, the thickness of the inorganic vapor deposited layer made of silicon oxide is preferably 30 Å to 3000 Å, more preferably 100 Å to 300 Å.
In addition, in the above, in the case of an inorganic vapor deposited layer consisting of a metal oxide, a metal nitride, or a metal carbide, if the thickness of the inorganic vapor deposited layer exceeds the above range, cracks etc. will easily occur in the inorganic vapor deposited layer. This is not preferable because there is a risk that the barrier properties will deteriorate due to warping, and the material cost will increase. Moreover, if it is less than the above range, it is not preferable because it tends to be difficult to exhibit oxygen barrier properties.

[Inorganic vapor deposited layer transfer body]
The inorganic vapor-deposited layer transfer body is a laminate including an inorganic vapor-deposited layer and an inorganic vapor-deposited layer support material, and optionally includes an adhesive layer on the surface of the inorganic vapor-deposited layer on the opposite side of the inorganic vapor-deposited layer support material. A release layer can be included between the inorganic deposited layer and the inorganic deposited layer support.
When transferring the inorganic vapor-deposited layer to the paper base material, the inorganic vapor-deposited layer is adhered to the paper base material via the adhesive layer, and then the inorganic vapor-deposited layer support material is peeled off. If the peelability at this time is insufficient, it is preferable to include a peeling layer between the inorganic vapor deposited layer and the inorganic vapor deposited layer support material so that the inorganic vapor deposited layer support material can be easily peeled off.
In order to strengthen the adhesive strength between the inorganic vapor deposited layer and the adhesive layer, the surface of the inorganic vapor deposited layer may be subjected to corona discharge treatment, ozone treatment, plasma treatment, glow discharge treatment, sandblasting treatment, etc. as necessary. The surface treatment layer can also be formed by performing a physical surface treatment or a chemical surface treatment such as an oxidation treatment using chemicals in advance.

In the inorganic vapor deposited layer transfer body, methods for forming the inorganic vapor deposited layer on the inorganic vapor deposited layer support material include, for example, a vacuum vapor deposition method, a sputtering method, an ion spray method using the inorganic compound constituting the inorganic vapor deposited layer as a raw material. physical vapor deposition method (PVD method), such as the cluster ion beam method, or chemical vapor deposition method, such as plasma chemical vapor deposition method, thermal chemical vapor deposition method, or photochemical vapor deposition method. An inorganic vapor deposition layer can be formed on an inorganic vapor deposition layer support material using a chemical vapor deposition method, a CVD method, or the like.

More specifically, in the above-mentioned PVD method, for example, a winding type vapor deposition machine is used, and the resin film released from the unwinding roll is put into the vapor deposition chamber in a vacuum chamber, and here, The vapor deposition source heated in the crucible is evaporated, and if necessary, an inorganic vapor deposition layer is formed on the resin film on the cooled coating drum through a mask while blowing out oxygen etc. from the oxygen outlet. Then, the inorganic vapor-deposited layer transfer body according to the present invention can be manufactured by winding it up on a winding roll.

On the other hand, in the above-mentioned CVD method, the surface of the inorganic vapor deposition layer support material fed out from the unwinding roll arranged in the vapor deposition chamber is cooled in the vapor deposition chamber, and then supplied from the vapor deposition raw material volatilization supply device on the circumferential surface of the electrode drum. For example, by introducing a mixed gas consisting of an organic silicon compound as a monomer gas, oxygen gas, an inert gas, etc., an inorganic vapor deposited layer transfer body can be produced in which an inorganic vapor deposited layer of silicon oxide or the like is formed by plasma. .

When forming the above-mentioned inorganic vapor deposited layer, the surface of the inorganic vapor deposited layer support material is cleaned by pre-treatment such as _SiO Close adhesion to the surface of the vapor deposited layer support material can be improved.
Furthermore, if two or more inorganic vapor deposition layers are continuously laminated using a plasma chemical vapor deposition apparatus consisting of at least two film forming chambers, continuous vapor deposition can be performed without exposing the inorganic vapor deposition layer to the atmosphere. It is possible to prevent foreign matter, dust, etc. that cause cracks from entering the inorganic vapor deposited layer, and to improve gas barrier properties.
Furthermore, if the inorganic vapor deposited layers are multilayered with two or more different compositions, since the inorganic vapor deposited layers are discontinuous layers with different compositions, the permeation of oxygen gas, water vapor, etc. can be suppressed more efficiently.

(Peeling layer)
The peeling layer is a layer for facilitating peeling off of the inorganic vapor-deposited layer support material.
When the inorganic vapor deposited layer support material is peeled off, the release layer may be peeled off together with the inorganic vapor deposited layer support material, and is transferred to the barrier paper together with the inorganic vapor deposited layer to function as a surface protective layer that protects the inorganic vapor deposited layer. It's okay.
The release layer is not particularly limited as long as it exhibits a well-balanced adhesive strength to achieve transfer of the inorganic vapor deposited layer, but preferably contains a resin and/or wax.
The resin is preferably a polyester resin, an acrylic resin, a silicone resin, a polyvinyl butyral resin, an acetal resin, etc., and one or more of these resins can be contained. Among the above, polyester resins and acrylic resins are particularly preferred.
The wax is preferably carbana wax, paraffin wax, polyethylene wax, polypropylene wax, etc., and one or more of these waxes may be contained. Among the above, polyethylene wax is particularly preferred.
The thickness of the release layer is preferably 0.2 g/m ² or more and 5.0 g/m ² or less.

When the inorganic vapor deposited layer is transferred to the adhesive layer on the paper base side and the inorganic vapor deposited layer supporting material is peeled off, if the release layer remains on the inorganic vapor deposited layer supporting material side, the release layer and the inorganic vapor deposited layer are The peel strength (adhesive strength) with the support material is preferably one of classifications 0 to 3 in the cross-cut test of JIS K5600-5-6.
Furthermore, when the inorganic vapor-deposited layer support material is peeled off and the release layer is transferred to a barrier paper together with the inorganic vapor-deposited layer for transfer, the peel strength between the release layer and the inorganic vapor-deposited layer support material is It is necessary that the adhesive strength is lower than the adhesive strength between the adhesive layer and the inorganic vapor deposited layer, and it is preferably classified as Class 4 or 5 in the cross-cut test of JIS K5600-5-6.

(Inorganic vapor deposition layer support material)
The supporting material for the inorganic vapor deposited layer is preferably a film made of resin.
The inorganic vapor deposited layer support material may be composed of one layer, or may be composed of two or more layers having the same or different compositions and laminated by any laminating means.
The supporting material for the inorganic vapor deposited layer is one that has excellent mechanical, physical, chemical, and other properties to withstand the process of forming the inorganic vapor deposited layer, and is especially strong and tough. It is preferable to use a material having heat resistance.
The supporting material for the inorganic vapor deposited layer preferably has supportability, and may be either an unstretched film or a stretched film stretched uniaxially or biaxially.

Suitable resins contained in the inorganic vapor deposited layer support material include, for example, polyester resins such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT); various nylons, especially polyamides such as aromatic polyamides such as nylon MXD6; Resin: Polyolefin resin such as polyethylene resin, polypropylene resin, polybutene resin, cyclic polyolefin resin; Polystyrene resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin) Polystyrene resins such as; polyvinyl chloride resins; polyvinylidene chloride resins (PVDC); polycarbonate resins; polyimide resins; polyamideimide resins; diaryl phthalate resins; silicone resins; polysulfone resins; polyphenylene sulfide resins Polyether sulfone resin; Polyurethane resin; Cellulose resin; Poly(meth)acrylic resin; Acetal resin; Fluorine resin; Ethylene-vinyl acetate copolymer; Ethylene-vinyl alcohol copolymer (EVOH); Examples include polyvinyl alcohol; polyacrylonitrile; and others. These resins may be used alone or in combination of two or more, or may be used in multiple layers containing different types of resins.
Among these, it is particularly preferable to contain a polyester resin and/or a polyamide resin, and PET is particularly preferable.

≪Printing layer≫
The printing layer may contain, for example, letters, numbers, figures, symbols, patterns, patterns, etc., for decoration, display of contents, display of expiration date, display of manufacturer, seller, etc., and for imparting aesthetic appearance. It visually shows a design pattern such as, and can form a desired design pattern.
The printing layer is preferably formed by a printing method such as a gravure printing method or a flexographic printing method. The printing layer may be provided on the entire surface of the printing surface, or may be provided on a part of the surface.

≪Reinforcement layer≫
The reinforcing layer is a layer that imparts mechanical strength, deformation resistance, drop impact resistance, pinhole resistance, heat resistance, sealability, quality maintenance, workability, hygiene, etc. to the barrier paper. .
The reinforcing layer may be formed from any of extrusion-formed or inflation-formed resin films, resin coating films, synthetic paper, and the like.

Specifically, the resin contained in the reinforcing layer includes, for example, low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer. Coalescence, ionomer resin, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid or methacrylic acid copolymer, methylpentene polymer, polybutene resin, polyvinyl chloride resin, polyvinyl acetate resin, polyvinylidene chloride resin , vinyl chloride-vinylidene chloride copolymer, poly(meth)acrylic resin, polyacrylonitrile resin, polystyrene resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS) polyester resins, polyamide resins, polycarbonate resins, polyvinyl alcohol resins, saponified ethylene-vinyl acetate copolymers, fluorine resins, diene resins, polyacetal resins, polyurethane resins, cellulose, Known resins such as nitrocellulose and others can be used.
Further, the above-mentioned resin film can be used either unstretched or uniaxially or biaxially stretched.
The thickness of the reinforcing layer is not particularly limited, but can be selected from a range of about 1 μm to 300 μm.

≪Functional layer≫
As a functional layer, it has barrier properties against oxygen gas, water vapor, etc., and/or has low adsorption of flavor components contained in the contents to be filled and packaged, and is rich in aroma retention, etc., and also does not cause off-taste, off-odor, etc. For example, a layer made of a resin that has a property that does not exist and can be extruded, and a layer made of a light-shielding material (light-shielding layer).

Specifically, the above resins include, for example, polyacrylic resin, polymethacrylic resin, polyacrylonitrile resin, polymethacrylonitrile resin, polystyrene resin, polycarbonate resin, polyethylene terephthalate resin, or its ethylene and/or a resin in which a part of the terephthalate component is copolymerized or modified with other di- or higher polyhydric alcohol components or dicarboxylic acid components, polyester resins such as polyethylene naphthalate resins, polyamide resins, ethylene- Resins such as saponified vinyl acetate copolymers, polyvinyl alcohol resins, polyvinyl chloride resins, polyvinylidene chloride resins, and others can be used.

Among the above resins, it is preferable to use resins that have aroma retention properties and barrier properties against oxygen gas or water vapor, etc. Specifically, examples include saponified ethylene-vinyl acetate copolymers, polyamide It is preferable to use resin, polyacrylonitrile-based resin, polyester-based resin, etc., which is rich in aroma retention properties, barrier properties, etc.

The light shielding layer is a layer provided to prevent ultraviolet rays and/or visible light from reaching the contents.
The light-shielding layer is made of white ink whose main component is titanium oxide, etc., black ink whose main component is carbon black, etc., gray ink whose main component is aluminum paste, or colored resin with a colorant that blocks light by adding pigments, dyes, etc. It can be formed using a film, metal foil, metal vapor deposition film, or the like.
Note that, as described above, when a metal foil such as aluminum foil is used as the barrier layer, the barrier layer can also serve as a light-shielding layer.
These light-shielding materials can be used alone or in combination of two or more.
When white ink, black ink, or gray ink is used, the thickness of the light shielding layer is preferably 4 μm or more and 12 μm or less, more preferably 5 μm or more and 9 μm or less.
In the case of aluminum foil, it is preferably 5 μm to 30 μm, in the case of a metal vapor deposited film, it is preferably 50 Å to 3000 Å, more preferably 100 Å to 1000 Å, and in the case of a colorant-colored resin film, it is preferably 5 μm to 300 μm, and 10 μm to 100 μm is more preferable.

[Method for producing barrier paper]
An example of a method for producing barrier paper is shown in FIG. 4.
First, the adhesive layer 4 is formed on one side of the paper base layer 3.
Then, the 5 sides of the inorganic vapor deposited layer of the separately prepared inorganic vapor deposited layer transfer body 7 (layer structure: inorganic vapor deposited layer 5/inorganic vapor deposited layer support material 8) are stacked and bonded so as to face the adhesive layer 4. and laminated to produce a barrier paper intermediate.
Next, the inorganic vapor deposited layer support material 8 is peeled off to obtain the barrier paper 1 (layer structure: inorganic vapor deposited layer 5/adhesive layer 4/paper base layer 3).

<<Barrier paper laminate>>
The barrier paper laminate is a laminate made from the barrier paper of the present invention, and may further include layers having various functions as necessary.
The barrier paper laminate can then be used to make, for example, a barrier wrapping paper material.
Barrier paper laminates, like barrier paper, have a simple layer structure, but have excellent barrier properties against oxygen gas and water vapor, have a high content of paper materials, a low content of plastic materials and metal elements, and have low content. It can also be used in a wide range of applications where objects come into direct contact.

The present invention will be explained in more detail with reference to the following Examples and Comparative Examples, but the present invention is not limited only to these Examples.

<Raw materials>
The main raw materials used in the examples are as follows.

[Paper base material]
-Paper base material A: Ryuoh coat, manufactured by Daio Paper Co., Ltd. Basis weight 55g/m ² , thickness 49μm, single-sided coated product.
・Paper base material B: Ryuoh coat, manufactured by Daio Paper Co., Ltd. Basis weight 80g/m ² , thickness 74μm, single-sided coated product.

[glue]
- Adhesive A: Isocyanate-based dry laminating adhesive manufactured by Rock Paint Co., Ltd., Ru40/H-1 = 15/2 mass ratio. When in use, adhere using the dry lamination method.
- Adhesive B: Solvent-type barrier adhesive manufactured by DIC Corporation, Paslim (base material VM001/curing agent 108CP). When in use, adhere using the dry lamination method.
- Adhesive C: Solvent-free barrier adhesive manufactured by DIC Corporation, Paslim (base agent NSRD011/curing agent NSRD006). When in use, it is adhered using a non-solvent laminating method.

[Preparation of inorganic vapor deposited layer transfer body]
(Preparation of inorganic vapor deposited layer transfer body A)
A diluted release agent solution (release agent k-45-3: ethyl acetate = 1:1 mass ratio mixture manufactured by Showa Ink) was applied to the corona-treated surface of a PET film (manufactured by Toyobo, thickness 12 μm, one side corona-treated product). It was coated by a bar coating method so that the layer thickness after drying was 1.0 g/m ² and dried in an oven at 80° C. for 1 minute to form a release layer to obtain a release base material.
Next, an aluminum vapor-deposited layer was formed as an inorganic vapor-deposited layer on the release layer by physical vapor deposition to obtain an inorganic vapor-deposited layer transfer body A having the following layer structure.
Layer structure: PET (12 μm) / release layer (1.0 g/m ² ) / aluminum vapor deposited layer (40 nm)

(Preparation of inorganic vapor deposited layer transfer body B)
Except for forming an aluminum oxide vapor deposited layer as the inorganic vapor deposited layer, an inorganic vapor deposited layer transfer material B having the following layer structure was obtained in the same manner as the inorganic vapor deposited layer transfer material A.
Layer structure: PET (12 μm) / release layer (1.0 g/m ² ) / aluminum oxide vapor deposited layer (20 nm)

(Preparation of inorganic vapor deposited layer transfer body C)
An inorganic vapor deposited layer transfer material C having the following layer structure was obtained by the same operation as the inorganic vapor deposited layer transfer material A except that a silicon oxide vapor deposited layer was formed as the inorganic vapor deposition layer by chemical vapor deposition.
Layer configuration: PET (12 μm)/release layer (1.0 g/m ² )/silicon oxide vapor deposited layer (20 nm)

[Example 1] (Adhesion by dry lamination method)
Step 1: Adhesive A was applied to the coated surface of a sheet of paper base material A (A4 size) so that the weight after drying was 3.0 g/m ² and dried.
Step 2: The surface coated with the adhesive A formed above and the surface of the inorganic vapor deposited layer of the inorganic vapor deposited layer transfer body A (A4 size) of a single sheet are bonded together facing each other, and laminated by applying pressure at 0.5 MPa. Then, aging was performed at 40° C. for 3 days to obtain a sheet barrier paper intermediate having the following layer structure.
Layer structure: paper base layer [paper base material/coating layer]/adhesive layer/inorganic vapor deposited layer/peel layer/inorganic vapor deposited layer support material Step 3: Inorganic vapor deposited layer support material in the barrier paper intermediate obtained above was peeled off to obtain a sheet barrier paper having the following layer structure, and various evaluations were performed.
Layer structure: paper base layer [paper base material/coating layer]/adhesive layer/inorganic vapor deposition layer/peel layer

[Example 2, 3, 5]
Barrier paper was obtained and evaluated in the same manner as in Example 1, except that the type of adhesive, the thickness of the adhesive layer, and the paper base material were selected according to the descriptions in Tables 1 and 2. Ta.

[Example 4] (Adhesion by non-solvent laminating method)
Form an adhesive layer with adhesive C on the coated surface of paper base material A so that the weight is 3.0 g/m ² , and paste it with the inorganic vapor deposited layer surface for transfer of inorganic vapor deposited layer transfer body A facing. They were laminated together and then aged at 40°C for 3 days to obtain a barrier paper intermediate having the following layer structure.
Layer configuration: paper base layer [paper base material/coating layer]/adhesive layer/inorganic vapor deposited layer/peel layer/inorganic vapor deposited layer support material.Then, the inorganic vapor deposited layer support material in the barrier paper intermediate is peeled off, An inorganic vapor deposited layer was formed by transfer to obtain a barrier paper having the following layer structure, and various evaluations were performed.
Layer structure: paper base layer [paper base material/coating layer]/adhesive layer/inorganic vapor deposition layer (transfer)/peel layer

[Example 6, 7]
The same procedure as in Example 1 was carried out, except that the type of adhesive, the thickness of the adhesive layer, and the paper base material were selected according to the description in Table 2, and the adhesive coated surface was formed on the non-coated surface of the paper base material. A barrier paper having the following layer structure was obtained by the same operation and evaluated in the same manner.
Layer structure: paper base layer [coat layer/paper base material]/adhesive layer/inorganic vapor deposition layer (transfer)/peel layer

[Example 8, 9]
A barrier paper was obtained in the same manner as in Example 1, except that inorganic vapor deposited layer transfer material A was changed to inorganic vapor deposited layer transfer material B or inorganic vapor deposited layer transfer material C according to the description in Table 2. was evaluated.

[Comparative Examples 1 to 3]
The inorganic vapor deposited layer type was selected according to the description in Table 3, and the inorganic vapor deposited layer was directly formed on the coated surface of the paper base material 1 by chemical vapor deposition to obtain a laminate having the following layer structure. Evaluation was performed in the same manner as in Example 1.
Layer structure: paper base layer [paper base material/coating layer]/inorganic vapor deposition layer (direct vapor deposition)

<Result summary>
The barrier paper of the present invention exhibited good adhesion of the inorganic vapor deposited layer and good gas barrier properties.
On the other hand, the laminate of the comparative example, which had a directly formed inorganic vapor deposited layer directly vapor deposited on the paper base material instead of an inorganic vapor deposited layer, had poor results in either the adhesion or gas barrier properties of the directly formed inorganic vapor deposited layer. Indicated.

<Evaluation method>

[Classification of interfacial adhesion of inorganic vapor deposited layer]
A cross-cut test was conducted on the obtained barrier paper in accordance with JIS K5600-5-6 to evaluate the interfacial adhesion of the inorganic vapor deposited layer (adhesion of the inorganic vapor deposited layer/adhesive layer interface) and classify it. .
Using a cross-cut jig to create a total of 25 grids (5 x 5 grids each 2 mm on a side), cut 25 grids (2 mm on a side) on the inorganic vapor deposition layer side of the barrier paper. The eyes were formed by a single blade.
Next, cellophane tape (width 15 mm x length 75 mm) was attached so as to cover the entire grid formed above.
Then, using Tensilon, the attached tape was peeled off from the edge at a rate of 3 mm/min, the degree of peeling of the inorganic vapor deposited layer was visually observed, and the results were classified according to the following evaluation criteria.
Category 0: The edges of the cut are completely smooth and there is no peeling on any grid.
Category 1: There is small peeling of the paint film at the intersection of cuts. However, the cross-cut portion is clearly affected by no more than 5%.
Category 2: Peeling of the coating along the cut edges and/or at intersections. The cross-cut area clearly affects between 5% and 15%.
Category 3: The paint film is partially or completely peeled off along the edges of the cut, and/or various parts of the eye are partially or completely peeled off. The cross-cut area is affected by more than 15% and less than 35%.
Category 4: The paint film has partially or completely peeled off along the edge of the cut, and/or some spots have partially or completely peeled off. The cross-cut area is affected within a range that clearly does not exceed 35%.
Category 5: Any level of peeling that cannot be classified even in Category 4.

[Oxygen permeability]
MOCON The oxygen permeability of the laminate at 90% at 23° C. was measured using a Mocon oxygen permeability measuring device manufactured by Hitachi High-Tech.
"Fail" in the table indicates that the value was above the measurement limit (200 cc/m ² /day/atm).
[Water vapor permeability]
MOCON The water vapor permeability of the laminate at 40°C and 90% was measured using a Mocon oxygen permeability measurement device manufactured by Hitachi High-Tech.
"Fail" in the table indicates that the value was above the measurement limit (50 g/m ² /day).

1 Barrier paper 2 Barrier paper intermediate 3 Paper base layer 4 Adhesive layer 5 Inorganic vapor deposited layer 6 Peeling layer 7 Inorganic vapor deposited layer transfer body 8 Inorganic vapor deposited layer support material 9 Printing layer

30 Barrier paper production system (dry lamination type)
31 Paper base material unwinding part 31a Paper base material 32 Adhesive coating part 32a Paper base material with adhesive layer 33 Drying zone 34 Inorganic vapor deposited layer transfer body unwinding part 34a Inorganic vapor deposited layer transfer body 35 Laminating part 35a Rubber roll 35b Metal Roll 35c Barrier paper intermediate 36 Peeling parts 36a, 36b Release roll 37 Barrier paper winding part 37a Barrier paper 38 Inorganic vapor deposition layer support material winding part 38a Inorganic vapor deposition layer support material

Claims (12)

A method for producing barrier paper having a layered structure in which at least a paper base layer, an adhesive layer, and an inorganic vapor deposition layer are laminated adjacently in this order,
The paper base layer has a basis weight of 50 g/m ² to 600 g/m ² ,
The thickness ratio occupied by the paper base layer in the barrier paper is 70% or more and 99% or less,
A method for producing barrier paper, comprising at least the following steps 1 to 3,
Step 1) Forming an adhesive layer on the surface to be bonded of the paper base layer to produce a paper base layer with an adhesive layer,
Step 2) The adhesive layer-attached paper base layer obtained in Step 1 and the inorganic vapor-deposited layer donor having an inorganic vapor-deposited layer and an inorganic vapor-deposited layer support layer are placed so that the adhesive layer and the inorganic vapor-deposited layer face each other. A step of laminating layers to produce a barrier paper intermediate,
Step 3) A step of peeling off the inorganic vapor deposited layer support layer from the barrier paper intermediate obtained in Step 2 to produce the barrier paper. The inorganic compound constituting the inorganic vapor deposited layer is a metal oxide, metal nitride or metal carbide,
The method for manufacturing barrier paper according to claim 1. The thickness of the paper base layer is 5 μm or more and 200 μm or less,
The method for manufacturing barrier paper according to claim 1 or 2. The thickness of the adhesive layer is 1 μm or more and 20 μm or less,
The method for producing barrier paper according to any one of claims 1 to 3. The barrier paper has an oxygen permeability of 0.01 cc/m ² /24 hr/atm or more and 10 cc/m ² /24 hr/atm or less at 23° C. 90%,
The water vapor permeability at 40° C. 90% is 0.01 g/m ² /24 hr or more and 20 g/m ² /24 hr or less,
The method for producing barrier paper according to any one of claims 1 to 4 . The interlayer adhesion strength between the adhesive layer and the inorganic vapor deposition layer is in any one of classifications 0 to 3 in the cross-cut test of JIS K5600-5-6.
The method for producing barrier paper according to any one of claims 1 to 5. The inorganic vapor deposited layer donor further has a release layer between the inorganic vapor deposited layer and the peelable inorganic vapor deposited layer support layer.
The method for producing barrier paper according to any one of claims 1 to 6 . The adhesive layer is a layer formed using a urethane resin composition,
The urethane resin composition contains a polyol and an isocyanate compound,
The polyol has two or more hydroxyl groups in one molecule, has a polyester structure part and/or a polyester polyurethane structure part in the main skeleton,
The polyhydric carboxylic acid derived structural part constituting the polyester structural part and/or the polyester polyurethane structural part contains an o-aromatic dicarboxylic acid derived structural part,
The isocyanate compound has two or more isocyanate groups in one molecule,
The method for producing barrier paper according to any one of claims 1 to 7 . A method for producing a barrier paper intermediate having a layer structure in which at least a paper base layer, an adhesive layer, an inorganic vapor deposited layer, and an inorganic vapor deposited layer support layer are stacked in contact with each other in this order,
The paper base layer has a basis weight of 50 g/m ² to 600 g/m ² ,
The thickness ratio occupied by the paper base layer in the laminate obtained by removing the inorganic vapor deposited layer support layer from the barrier paper intermediate is 70% or more and 99% or less,
A method for producing a barrier paper intermediate , comprising at least the following steps 1 and 2,
Step 1) Forming an adhesive layer on the paper base layer to produce a paper base layer with an adhesive layer,
Step 2) An inorganic vapor-deposited layer donor having an inorganic vapor-deposited layer and an inorganic vapor-deposited layer support layer and the adhesive layer-attached paper base layer obtained in Step 1 are placed so that the inorganic vapor-deposited layer and the adhesive layer face each other. The process of laminating layers to create a barrier paper intermediate. The inorganic vapor deposited layer donor further has a release layer between the inorganic vapor deposited layer and the peelable inorganic vapor deposited layer support layer.
The method for producing a barrier paper intermediate according to claim 9 . The adhesive layer is a layer formed using a urethane resin composition,
The urethane resin composition contains a polyol and an isocyanate compound,
The polyol has two or more hydroxyl groups in one molecule, has a polyester structure part and/or a polyester polyurethane structure part in the main skeleton,
The polyhydric carboxylic acid derived structural part constituting the polyester structural part and/or the polyester polyurethane structural part contains an o-aromatic dicarboxylic acid derived structural part,
The isocyanate compound has two or more isocyanate groups in one molecule,
The method for producing a barrier paper intermediate according to claim 9 or 10 . The inorganic compound constituting the inorganic vapor deposited layer is a metal oxide, metal nitride or metal carbide,
A method for producing a barrier paper intermediate according to any one of claims 9 to 11.

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