JP2003237828A - Flexible packaging bag - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a flexible packaging bag which is excellent in physical properties such as strength, in particular, in barrier property to prevent permeation of gaseous oxygen, steam, etc., and in light shading property, has filling and packaging suitability and preserving suitability of the content, and is excellent in disposability and environmental suitability without generating any harmful substances when performing incineration disposal after the use. <P>SOLUTION: The flexible packaging bag is formed of a laminate in which at least three layers of a base material of barrier property having a vapor deposition film of inorganic oxide on one side of a base film, a layer of light shading property, and a heat-sealable resin layer, at least four layers of a base material of barrier property having a vapor deposition film of inorganic oxide on one side of a base film, a layer of light shading property, an intermediate base material, and a heat-sealable resin layer, or at least four layers of a surface base film, a layer of light shading property, a base material of barrier property having a vapor deposition film of inorganic oxide on one side of a base film, and a heat-sealable resin layer are successively stacked. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a flexible packaging bag,
More specifically, it has strength, weather resistance, heat resistance,
Excellent in various physical properties such as water resistance, heat seal, pinhole resistance, puncture resistance, etc. In particular, it has excellent barrier properties to prevent permeation of oxygen gas, water vapor, etc. The present invention relates to a flexible packaging bag that has suitability for filling and packing of contents, suitability for storage, etc., and further has excellent disposal suitability, environmental suitability, etc. without generating harmful substances when incinerated and disposed of after use. Is.

[0002]

2. Description of the Related Art Conventionally, for example, food and drink, fruit juice, juice
Su, drinking water, liquor, cooked food, seafood paste, frozen food,
For filling and packaging various food and drink products such as meat products, boiled foods, rice cakes, liquid soups, seasonings, etc., liquid detergents, cosmetics, chemical products, and other products, plastic films, metal foils, cellophane, Laminating materials such as packaging materials made of various forms by arbitrarily laminating other base materials such as
Proposed. Thus, in recent years, in the above-mentioned laminated material, as a barrier base material constituting the laminated material, a vapor deposition film of an inorganic oxide such as aluminum oxide or silicon oxide is also formed on one surface of a base material film made of a resin film or the like. Attention has been paid to a barrier substrate having a provided structure, and substrates having various forms have been developed and proposed. This one is oxygen gas,
It has excellent barrier properties that prevent the permeation of water vapor, etc., and also has excellent transparency. Also, after use, it does not generate harmful substances when incinerated and disposed of, and is suitable for disposal.
It is excellent in environmental suitability and the like, and its usage is expanded in various fields, and the demand amount thereof is expanding.

[0003]

However, as a barrier substrate, a substrate film made of the above resin film or the like is provided with a vapor deposition film of an inorganic oxide such as aluminum oxide or silicon oxide on one surface thereof. To form a desired laminated material by arbitrarily laminating this with other base materials, and then using the laminated material, and bag-making the bag-shaped container body. Then, in the case of producing a packaged product by filling and packaging the contents such as the desired food and drink in the bag-shaped container body, on one side of the base film made of the resin film or the like, The barrier substrate having a structure in which a vapor deposition film of an inorganic oxide such as aluminum oxide or silicon oxide is also provided,
Since this has transparency, for example, sunlight or fluorescent light or the like from the sun or a fluorescent lamp is transmitted, the transmitted light affects the contents, for example, the contents are decomposed or deteriorated, or fading, There is a problem that it causes photodegradation such as others. For this reason, there is a method of blocking the transmission of light by using, for example, an aluminum foil or a vapor deposition film of aluminum in combination with the above-mentioned barrier substrate to prevent light deterioration. A foil, a vapor-deposited film of aluminum or the like is extremely useful because it has a barrier property for preventing permeation of oxygen gas, water vapor and the like and also has a light blocking property, but an aluminum foil etc. lacks bending resistance and the like. Therefore, there is a problem that pinholes are likely to occur and the barrier property thereof is significantly impaired.Furthermore, when used as a packaging container and then disposed of as waste, for example, when disposed of by incineration or the like. , Metal such as aluminum remains, which may damage the incinerator, lacks suitability for disposal of the incinerator, causes problems such as environmental destruction, and lacks environmental suitability. It is not preferable from the fact that there is a cormorant problem. In addition, for example, a colored layer is combined with a barrier layer substrate having a structure in which a vapor deposition film of an inorganic oxide such as aluminum oxide or silicon oxide is also provided on one surface of a substrate film made of the above resin film or the like. However, in this case, the vapor-deposited film of an inorganic oxide such as aluminum oxide or silicon oxide, which constitutes the above-mentioned barrier base material, is an inorganic one. And, since it is made of glass and is extremely inert, therefore, simply on the surface of the deposited film of an inorganic oxide such as aluminum oxide or silicon oxide
Even if a colored layer is provided, both of them lack affinity and the like and are inferior in their dense adhesion, and for example, a phenomenon such as delamination between layers occurs, and the barrier substrate and the colored layer The laminated material containing is no longer capable of functioning as a packaging material or the like constituting a packaging container or the like, and is no longer useful. Therefore, the present invention has strength and the like, and is excellent in various physical properties such as weather resistance, heat resistance, water resistance, heat seal resistance, pinhole resistance, puncture resistance, and the like, and particularly oxygen. It has excellent barrier properties that prevent the permeation of gas, water vapor, etc., as well as excellent light-shielding properties, suitability for filling and packaging of contents, suitability for storage, etc. Furthermore, it produces toxic substances when incinerated and disposed of after use. It is an object of the present invention to provide a flexible packaging bag that is extremely excellent in disposal suitability, environmental suitability, and the like.

[0004]

Means for Solving the Problems As a result of various studies to solve the above problems, the present inventor first found that, for example, one surface of a base film made of the above resin film was oxidized. A vapor-deposited film of an inorganic oxide such as aluminum or silicon oxide is also provided to produce a barrier substrate, and then the surface of the vapor-deposited film of an inorganic oxide such as aluminum oxide or silicon oxide constituting the barrier substrate is For example, after a pretreatment such as corona discharge treatment or plasma treatment, a primer agent layer is formed with a primer agent containing a polyurethane resin or a polyester resin as a main component of the vehicle, and then the primer agent layer is formed. A desired printed pattern layer is provided on the agent layer, and then a white printed film layer of the white ink composition and a black printed film layer of the black ink composition are formed on the entire surface including the printed pattern layer. A light-shielding layer consisting of a layer, and further, the white print coating layer constituting the light-shielding layer also serves as a base layer of the print pattern layer, and then on the black print coating layer. , A heat-sealing resin layer is laminated,
A laminated material as a packaging material is produced, and then the laminated material is used to make a bag to produce a soft packaging bag, and then the flexible packaging bag is filled with a desired content such as food and drink. Was filled and packaged to produce a packaged product, which had strength and the like, and
Weather resistance, heat resistance, water resistance, heat seal resistance, pin hoe resistance
Excellent in various physical properties such as resistance, puncture resistance, etc.
Oxygen gas, excellent in barrier properties to prevent permeation of water vapor and the like, and excellent in light blocking property, for example, to prevent transmission of sunlight or fluorescence by the sun or fluorescent lamps, the contents are decomposed or altered, or It prevents the occurrence of photodegradation such as fading, fading, etc., and has the suitability for filling and packaging of contents, the suitability for storage, etc. Furthermore, it is disposed without generating harmful substances when incinerated and disposed of after use. The present invention has been completed by finding that it is possible to produce a flexible packaging bag having extremely excellent processing suitability and environmental suitability.

That is, according to the present invention, at least a barrier substrate having a vapor-deposited inorganic oxide film on one surface of the substrate film, a light-blocking layer, and a heat-sealing resin layer are provided. Three
Layer, at least four layers of a barrier substrate having an inorganic oxide vapor deposition film on one surface of the substrate film, a light blocking layer, an intermediate substrate, and a heat sealable resin layer Or, at least, a surface base film, a light blocking layer, a barrier base material having a vapor deposition film of an inorganic oxide provided on one surface of the base film, and a heat sealable resin layer The present invention relates to a soft packaging bag, which is made by forming a laminated material in which four layers are sequentially laminated.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The flexible packaging bag according to the present invention will be described in more detail below with reference to the drawings. First, a layer structure of a laminated material constituting a flexible packaging bag according to the present invention will be described with reference to the drawings by exemplifying a few examples thereof, and FIGS. 1, 2, 3, 4, 5, and 6 7A and 7B are schematic cross-sectional views showing the layer configurations of a few examples of the laminated material constituting the flexible packaging bag according to the present invention.
FIG. 2 is a schematic perspective view showing a configuration of an example of a soft packaging bag according to the present invention, which is manufactured by using the laminated material shown in FIG. 1 to make a bag.

First, as shown in FIG. 1, the laminated material A constituting the flexible packaging bag according to the present invention is at least:
The substrate film 1 has a structure in which a barrier substrate 3 provided with an inorganic oxide vapor deposition film 2 on one surface thereof, a light blocking layer 4, and a heat-sealable resin layer 5 are sequentially laminated. This is the basic structure. Next, as a specific example of the laminated material constituting the flexible packaging bag according to the present invention, as shown in FIG. 2, at least one surface of the base film 1 is provided with the vapor deposition film 2 of the inorganic oxide. A barrier base material 3, a desired pretreatment layer 6 previously provided on the surface of the vapor-deposited film 2 of the inorganic oxide constituting the barrier base material by corona discharge treatment or plasma treatment, and a primer by a primer agent. -Lamination material A ₁ having a structure in which the agent layer 7, the printed pattern layer 8, the light-shielding layer 4, and the heat-sealable resin layer 5 are sequentially laminated.
Can be illustrated. Further, as another specific example of the laminated material constituting the flexible packaging bag according to the present invention, as shown in FIG. 3, at least one surface of the substrate film 1 is provided with the vapor deposition film 2 of the inorganic oxide. Barrier substrate 3 provided and vapor deposition film 2 of inorganic oxide constituting the barrier substrate
Desired pretreatment layer 6 provided in advance by corona discharge treatment, plasma treatment or the like, a primer agent layer 7 with a primer agent, a printed pattern layer 8, a light blocking layer 4, and an intermediate base material 9 And the heat-sealable resin layer 5 are sequentially laminated, and a laminated material A ₂ can be exemplified. Furthermore, when another specific example is illustrated about the laminated material which comprises the flexible packaging bag concerning this invention, as shown in FIG. 4, at least the surface base material 10, the printed pattern layer 8, and the light blocking layer. 4, a barrier substrate 3 having an inorganic oxide vapor deposition film 2 provided on one surface of the substrate film 1, and a corona discharge treatment on the surface of the inorganic oxide vapor deposition film 2 constituting the barrier substrate. Alternatively, a desired pretreatment layer 6 previously provided by plasma treatment or the like
And a laminate material A ₃ having a constitution in which a primer agent layer 7 made of a primer agent and a heat-sealable resin layer 5 are sequentially laminated.

The above examples are examples of the laminated materials constituting the flexible packaging bag according to the present invention, and the present invention is not limited thereto. In the present invention, in the laminated material shown in FIGS. 1 to 4, as the light blocking layer, as shown in FIG.
The light-shielding layer 4 composed of a printed film layer 4a of an ink composition, specifically, a printed film composed of two layers of a white printed film layer 4b of a white ink composition and a black printed film layer 4c of a black ink composition. The layer 4a, and further, the white printed film layer 4b constituting the printed film layer 4a described above is positioned so as to face the surface of the printed pattern layer 8 and also has the function of the underlying layer of the printed pattern layer 8. It is desirable that the light shielding layer 4 is Thus, in the present invention, a printing film layer of the ink composition as described above, specifically two-layer printing of a white printing film layer of a white ink composition and a black printing film layer of a black ink composition. By forming the light-shielding layer from the coating layer, the printed pattern such as desired characters, symbols, pictures, figures, etc. constituting the printed pattern layer can be made clear and excellent in light-shielding property. Prevents the passage of sunlight or fluorescence from lights, etc., causing the contents to decompose or deteriorate, or fading,
It is possible to prevent the occurrence of photodegradation such as other, further, after using the flexible packaging bag according to the present invention as a packaging container, without generating harmful substances or the like when incinerated and disposed of. It is extremely excellent in disposal suitability and environmental suitability.

Further, in the present invention, the above-mentioned FIGS.
Although not shown, the laminated material shown in (1) can be laminated with other base materials depending on the purpose of use, application, etc. to design and manufacture laminated materials of various forms. . Further, although not shown, in the present invention, for example, regarding the laminated material shown in FIGS. 1 to 4 described above, the vapor deposition film of the inorganic oxide is not limited to a single-layer film consisting of one layer of the vapor deposition film of the inorganic oxide. It can also be composed of a multilayer film composed of two or more layers of a vapor deposition film of an inorganic oxide. Further, in the present invention, in the laminated material shown in FIG. 4, although not shown, when a barrier substrate having a vapor deposition film of an inorganic oxide provided on one surface of the substrate film is laminated, its barrier property is The surface of the vapor-deposited film of the inorganic oxide forming the substrate may be laminated either toward the outside or inside.

Next, in the present invention, the soft packaging bag according to the present invention, which is manufactured by using the above-mentioned laminated material and making the bag, will be explained by exemplifying an example thereof. As the flexible packaging bag, for example, the above-mentioned FIG.
An example of a soft packaging bag manufactured by using the laminated material A shown in FIG. 6 will be described. As shown in FIG. The surfaces of the tosyl resin layers 5 and 5 are made to face each other and overlap each other, and then the three ends of the periphery of the periphery are heat-sealed to seal the seal portion 1.
1, 11, 11 are formed and an opening 12 is formed above them.
Is provided to manufacture a three-way seal type bag-shaped container body B.
Thus, in the present invention, as shown in FIG. 7, for example, from the opening 12 of the three-way seal type bag-shaped container body B manufactured above, for example, food and drink, fruit juice, juice, Drinking water, liquor, cooked food, seafood paste, frozen food, meat products,
Filled with contents 13 consisting of various food and drink such as cooked foods, rice cakes, liquid soaps, seasonings, etc., liquid detergents, cosmetics, chemical products, and other articles, and then the end of the upper opening 12 It is possible to manufacture a packaged product C of various forms using the soft packaging bag B according to the present invention by heat-sealing the parts to form the upper seal part 14 and the like. .
In the present invention, needless to say, the soft packaging bag according to the present invention is not limited to the above-illustrated pouch shape illustrated above.
Three-way seal type, self-supporting type, gusset type,
It goes without saying that a flexible packaging bag having various shapes such as a square bottom type and the like can be manufactured. In addition, it goes without saying that in the present invention, the flexible packaging bag according to the present invention can be manufactured in the same manner as above by using the laminated material shown in FIGS.

Next, in the present invention, the materials constituting the flexible packaging bag according to the present invention, the manufacturing method, etc. will be described.
First, as the base material film forming the barrier base material constituting the soft packaging bag according to the present invention, these are the basic materials constituting the soft packaging bag, and further, the vapor deposition film of the inorganic oxide is retained. First, since it is a base material to be heat-treated during bag making, workability, etc., it is excellent in various physical properties such as weather resistance, heat resistance, water resistance, slipperiness, pinhole resistance, and the like. Use a resin film or sheet that can withstand the conditions for forming a vapor-deposited film of an inorganic oxide and can hold it well without impairing its characteristics, and that can satisfy other conditions. can do.
In the present invention, as the resin film or sheet, specifically, for example, a polyolefin resin such as a polyethylene resin or a polypropylene resin,
Cyclic polyolefin resin, polystyrene resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS
Resin), poly (meth) acrylic resin, polycarbonate
Resin, polyester resin such as polyethylene terephthalate and polyethylene naphthalate, polyamide resin such as various nylons, polyurethane resin, acetator
Films or sheets of various resins such as resin, cellulose resin, etc. can be used. In the present invention, among the above resin films or sheets, it is particularly preferable to use a polyester resin, a polyolefin resin, or a polyamide resin film or sheet.

In the present invention, as the film or sheet of the above-mentioned various resins, for example, one or more of the above-mentioned various resins are used, and the extrusion method, the cast molding method, the T-die method, the cutting method. Method, film formation method such as inflation method, etc., to form a film of each of the above resins alone, or multilayer coextrusion film formation using two or more kinds of resins. Film or sheet of various resins is produced by a method of forming a resin, and a method of forming a film by mixing 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 6 to 200 μm.
Position, more preferably about 9 to 100 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, 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, reinforcing agents, antistatic agents, pigments and the like can be used, and further, modifying resins and the like can also be used.

In the present invention, the surface of the film or sheet of various resins may have a desired surface in advance, if necessary, in order to improve the close adhesion property with the vapor deposition film of the inorganic oxide. A treatment layer can be provided. In the present invention, as the surface treatment layer, for example, corona discharge treatment, ozone treatment, low temperature plasma treatment using oxygen gas or nitrogen gas, glow discharge treatment, oxidation treatment using chemicals, 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 the film or sheet of various resins and the vapor deposition film of the inorganic oxide. In addition to the above, for example, a primer-coating agent layer, an under-coating agent layer, an anchor-coating agent layer, and an adhesive layer are previously formed on the surface of various resin films or sheets. Alternatively, 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, It is possible to use a resin composition containing a polyolefin resin such as polyethylene Aluha polypropylene or a copolymer or modified resin thereof, a cellulose resin, or the like as a vehicle main component.

Next, in the present invention, the vapor deposition film of an inorganic oxide forming the barrier substrate constituting the soft packaging bag of the present invention will be described. As the vapor deposition film of such an inorganic oxide, first, for example, Vapor deposition method, sputtering method, ion plating method, ion cluster beam method, and other physical vapor deposition methods (Physical Vapor Deposition).
Deposition method, PVD method) can be used. In the present invention, specifically, a metal oxide is used as a raw material, a vacuum vapor deposition method in which the metal oxide is heated and vapor-deposited on the substrate film, or a metal or a metal oxide is used as a raw material and oxygen An amorphous thin film of an inorganic oxide is formed by using an oxidation reaction deposition method of introducing and oxidizing and depositing it on a base film, and a plasma-assisted oxidation reaction deposition method of further assisting the oxidation reaction with plasma. be able to. 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.

Therefore, in the present invention, as the above-mentioned vapor deposition film of inorganic oxide, basically, any thin film obtained by vapor deposition of metal oxide can be used. For example, silicon (S
i), aluminum (Al), magnesium (Mg),
Calcium (Ca), potassium (K), tin (Sn),
Sodium (Na), boron (B), titanium (Ti),
A vapor deposition film of an oxide of a metal such as lead (Pb), zirconium (Zr), yttrium (Y) can be used. Thus, preferred are silicon (Si),
A vapor deposition film of an oxide of a metal such as aluminum (Al) can be given. The vapor deposition film of the above metal oxide can be referred to as a metal oxide such as silicon oxide, aluminum oxide, magnesium oxide and the like, and the notation is, for example, SiO _x , AlO _x , MgO. MO _X (However, as of _X, etc., in the formula, M represents a metal element,
The range of the value of X differs depending on the metal element. )
It is represented by. The range of the value of X is 0 to 2 for silicon (Si) and 0 to for aluminum (Al).
1.5, magnesium (Mg) is 0 to 1, calcium (Ca) is 0 to 1, potassium (K) is 0 to 0.5,
Tin (Sn) is 0 to 2, sodium (Na) is 0 to
0.5, boron (B) is 0 to 1, 5 and titanium (Ti)
Is 0 to 2, lead (Pb) is 0 to 1, zirconium (Z
r) can take a value in the range of 0 to 2, and yttrium (Y) can take a value in the range of 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. Further, the upper limit of the range of X is a completely oxidized value. In the present invention, in general, silicon (S
Other than i) and aluminum (Al), there are few examples used, and silicon (Si) has a value in the range of 1.0 to 2.0 and aluminum (Al) has 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, or the type of the metal oxide, and the like.
50 to 4000Å, preferably 100 to 1000Å
It is desirable to arbitrarily select and form within the range of the order.
Further, in the present invention, the metal used as the vapor deposition film of the inorganic oxide or the metal oxide used is 1
It is also possible to use one kind or a mixture of two or more kinds to form a vapor deposition film of an inorganic oxide mixed with different materials.

Next, in the present invention, a specific example of the method for forming the above-mentioned vapor-deposited film of an inorganic oxide will be given. FIG. 8 is a schematic configuration diagram showing an example of a winding type vacuum vapor deposition apparatus. . As shown in FIG. 8, the unwinding roll is set in the vacuum chamber-22 of the winding type vacuum deposition apparatus 21.
The base film 24 fed from the roll 23 is cooled by the guide rollers 25 and 26, and the coated drum 27 is cooled.
Will be guided to. Then, the vapor deposition source 29 heated by the crucible 28, for example, metal aluminum or aluminum oxide is evaporated on the substrate film 24 guided on the cooled coating drum 27, Further, if necessary, oxygen gas or the like is ejected from the oxygen gas outlet 30, and while supplying this, a vapor deposition film of an inorganic oxide such as aluminum oxide is formed through the masks 31 and 31. It is a thing. Then, in the present invention,
In the above, for example, the substrate film 24 on which a vapor deposition film of an inorganic oxide such as aluminum oxide is formed is wound around a winding roll 34 or the like via guide rolls 32, 33 or the like, and the inorganic material according to the present invention is obtained. The base film 24 having a vapor-deposited oxide film can be manufactured. Needless to say, the above-mentioned exemplification is one example, and the present invention is not limited thereby. In addition, in the present invention, first, a vapor deposition film of an inorganic oxide of the first layer is formed by using the above-described winding type vacuum vapor deposition device, and then, in the same manner, the vapor deposition film of the inorganic oxide is formed. On top of this, further form a vapor deposition film of inorganic oxide,
Alternatively, by using the above-described roll-up type vacuum vapor deposition device, the vapor deposition films of inorganic oxides are continuously formed by continuously connecting the two vapors to form an inorganic oxide film having two or more layers. It is possible to form a vapor deposition film of an object.

Next, in the present invention, the above-mentioned vapor-deposited film of inorganic oxide can be formed by, for example, a chemical vapor deposition method or the like. Chemical Vapor Deposition (Chemical Vapor Deposition) such as chemical vapor deposition and photochemical vapor deposition
It can be formed by using a method such as a position method or a CVD method. More specifically, on one surface of the base film,
A low temperature plasma is generated by using a monomer gas for vapor deposition such as an organosilicon compound as a raw material, an inert gas such as argon gas or helium gas as a carrier gas, and an oxygen gas or the like as an oxygen supply gas. 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 an apparatus or the like. In the above,
As the low temperature plasma generator, for example, a generator of high frequency plasma, pulse wave plasma, microwave plasma or the like may be used, and in the present invention,
In order to obtain highly active and stable plasma, it is desirable to use a high frequency plasma generator.

A specific 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. 9 shows the inorganic material by the plasma chemical vapor deposition method described above. 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 41--
The base film 44 is unwound from the unwinding roll 43 arranged inside the base 42, and the base film 44 is further cooled at a predetermined speed through the auxiliary roll 45.
Carry on the peripheral surface. Thus, in the present invention, oxygen gas, inert gas, monomer gas for vapor deposition of organic silicon compounds and the like are supplied from the gas supply devices 47 and 48, the raw material volatilization supply device 49 and the like, and from these, The mixed gas composition for vapor deposition was adjusted, and then the mixed gas composition for vapor deposition was introduced into the vacuum chamber-42 through the raw material supply nozzle 50, and then was conveyed onto the peripheral surface of the cooling / electrode drum 46. Plasma is generated by the glow discharge plasma 51 on the base film 44, and this is irradiated to form a vapor deposition film of an inorganic oxide such as silicon oxide to form a film.
In the present invention, at that time, the cooling / electrode drum 46
Is supplied with a predetermined electric power from a power source 52 arranged outside the chamber, and a magnet 53 is arranged in the vicinity of the cooling / electrode drum 46 to promote generation of plasma. Then, the base film 44 on which the vapor deposition film of the inorganic oxide such as silicon oxide is formed is guided by
Take up on the take-up roll 55 etc. via the rule 54 etc.,
It is possible to manufacture a substrate film having a vapor deposited film of an inorganic oxide according to the present invention. In the figure, 56 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, the inorganic oxide vapor deposition film may be not only one layer of the inorganic oxide vapor deposition film but also a multi-layered film in which two or more layers are laminated and used. The materials may be used alone or as a mixture of two or more kinds, and it is also possible to form a vapor deposition film of an inorganic oxide in which different materials are mixed.

In the above, the inside of the vacuum chamber is vacuumed.
The pressure is reduced by a pump and the degree of vacuum is 1 × 10. ^-1~ 1 x 10^-8To
rr position, preferably vacuum degree 1 × 10^-3~ 1 x 10^-7T
It is desirable to prepare it at the orr position. Also,
In the raw material volatilization supply device, the raw material organosilicon compound
Oxygen gas that volatilizes things and is supplied from the gas supply device,
It is mixed with an inert gas, etc.
It is introduced into the vacuum chamber via a cable.
In this case, the content of the organosilicon compound in the mixed gas is 1
-40%, oxygen gas content is 10-70%,
The content of active gas should be in the range of 10-60%
For example, an organic silicon compound, oxygen gas and an inert gas
The mixing ratio with the soot is about 1: 6: 5 to 1:17:14.
be able to. On the other hand, from the power supply to the cooling and electrode drum
Since a predetermined voltage is applied, the inside of the vacuum chamber
In the vicinity of the opening of the raw material supply nozzle and the cooling / electrode drum
A glow discharge plasma is generated, and this glow discharge plasma is generated.
Ma is derived from one or more gas components in a gas mixture.
In this state, the base film is kept constant
Transported at high speed and cooled by glow discharge plasma
On the base film on the peripheral surface of the electrode drum,
It is capable of forming a vapor deposition film of an inorganic oxide.
It The degree of vacuum in the vacuum chamber at this time is 1
× 10^-1~ 1 x 10^-FourTorr position, preferably vacuum degree
1 x 10^-1~ 1 x 10^-2Desirable to be adjusted to Torr position
Also, the transport speed of the base film is 10 to 30.
0m / quantile, preferably 50-150m / min
Is desirable.

[0021] In the above plasma chemical vapor deposition apparatus, the formation of the deposited film of an inorganic oxide such as silicon oxide, on the substrate film, SiO _X while the plasma raw material gas is oxidized with oxygen gas Since it is formed into a thin film in the form of, the vapor-deposited film of inorganic oxide such as silicon oxide is a dense, flexible, continuous layer with few gaps, and therefore is oxidized. The barrier property of a deposited film of an inorganic oxide such as silicon is much higher than that of a deposited film of an inorganic oxide such as silicon oxide formed by a conventional vacuum deposition method or the like, and a thin film thickness is sufficient. A barrier property can be obtained. Further, in the present invention, SiO _x
Since the surface of the base film is cleaned by plasma and polar groups and free radicals are generated on the surface of the base film, a vapor deposition film of an inorganic oxide such as silicon oxide and the base film are formed. It has an advantage that the dense adhesion property of is high. Furthermore, the degree of vacuum during formation of a continuous film of an inorganic oxide such as silicon oxide is 1 × 10 ^-1.
To 1 × 10 ^-4 Torr position, preferably 1 × 10 ^-1 to 1
Since it is adjusted to the position of × 10 ^-2 Torr, the degree of vacuum when forming a deposited film of an inorganic oxide such as silicon oxide by the conventional vacuum deposition method is set to the position of 1 × 10 ^-4 to 1 × 10 ^-5 Torr. Since the degree of vacuum is comparatively low, it is possible to shorten the time for setting the vacuum state when replacing the substrate film with the original film, to easily stabilize the degree of vacuum, and to stabilize the film forming process.

In the present invention, a 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 organic silicon compound and oxygen gas, and the like. 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 is mainly composed of silicon oxide, and further contains at least one compound of carbon, hydrogen, silicon or oxygen, or a 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
by performing elemental analysis of the vapor-deposited film of silicon oxide 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 description, 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 pretreatment layer provided on the surface of the vapor deposition film of the inorganic oxide constituting the barrier substrate as described above will be explained.
For example, corona discharge treatment, ozone treatment, low temperature plasma treatment using oxygen gas or nitrogen gas, glow discharge treatment, oxidation treatment using chemicals and the like, optionally subjected to pretreatment such as, for example, A corona treatment layer, an ozone treatment layer, a plasma treatment layer, an oxidation treatment layer, and the like can be formed and provided on the surface of the deposited film of the inorganic oxide. The above-mentioned pretreatment layer activates the surface of the vapor deposition film of inorganic oxide, and improves, for example, the close adhesion property with a primer agent layer, a printed pattern layer, a light blocking layer, etc. described later. It is a thing.

Next, in the present invention, the primer agent layer provided on the surface of the vapor-deposited film of the inorganic oxide which constitutes the above-mentioned barrier substrate will be explained. After providing a vapor deposition film of an inorganic oxide on one surface of the film, it is provided on the surface of the pretreatment layer of the vapor deposition film of the inorganic oxide to form a print pattern layer, a light blocking layer, and a heat seal resin. It is provided in order to enhance the dense adhesiveness when laminating layers and the like and to improve the laminating strength and the like. For the primer layer, first, a polyurethane resin or polyester resin is used as the main component of the vehicle, and 1 to 30% by weight of the polyurethane resin or polyester resin is added to the silane coupling agent 0. .05
About 10% by weight, preferably 0.1% by weight to 5% by weight
%, About 0.1 to 20% by weight of filler, preferably 1 to 1
0% by weight, and if necessary, stabilizers, curing agents, cross-linking agents, lubricants, UV absorbers, and other additives are optionally added, and solvents, diluents, etc. are added. The resin composition is prepared by thoroughly mixing.

Then, the resin composition prepared above is used, and this is used, for example, in a roll coat, a gravure coat,
A knife coat, dip coat, spray coat, or other coating method is used to coat the surface of the pretreatment layer of the inorganic oxide vapor-deposited film provided on one surface of the above-mentioned substrate film. Coating, and then the coating film is dried to remove the solvent, diluent and the like, and further, if necessary, aging treatment or the like to form the primer agent layer according to the present invention. You can In the present invention, the thickness of the primer layer is, for example, 0.1 g / m ^{2 to} 5.
0 g / m ² (dry state) is desirable. Thus, in the present invention, the primer agent layer as described above improves the dense adhesion and the like and improves the degree of elongation of the primer agent layer, for example, laminating or bag making. It is intended to improve suitability for post-processing such as processing and prevent the occurrence of cracks and the like in the vapor deposition film of inorganic oxide during the post-processing.

In the above, as the polyurethane resin constituting the above resin composition, for example, a polyurethane resin obtained by reacting a polyfunctional isocyanate with a compound containing a hydroxyl group can be used. Specifically, for example, aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate and polymethylene polyphenylene polyisocyanate.
Or a polyfunctional isocyanate such as an aliphatic polyisocyanate such as hexamethylene diisocyanate or xylylene diisocyanate, and a polyether polyol.
It is possible to use a one- or two-component curing type polyurethane resin obtained by a reaction with a hydroxyl group-containing compound such as resin, polyester polyol, polyacrylate polyol, and the like. Thus, in the present invention,
By using the polyurethane-based resin as described above, it is possible to improve the dense adhesion property and the elongation of the primer layer, and, for example, suitability for post-processing such as laminating or bag making. To prevent the occurrence of cracks and the like in the vapor-deposited film of an inorganic oxide during post-processing.

In the above, as the polyester resin constituting the above resin composition, for example, one or more aromatic saturated dicarboxylic acids having a benzene nucleus as a basic skeleton such as terephthalic acid and saturated A thermoplastic polyester resin produced by polycondensation with one or more divalent alcohols can be used. In the above, examples of the aromatic saturated dicarboxylic acid having a benzene nucleus as a basic skeleton include, for example, terephthalic acid, isophthalic acid, phthalic acid, diphenyl ether-
4,4-dicarboxylic acid, etc. can be used. Further, in the above, as the saturated divalent alcohol, ethylene glycol, propylene glycol, trimethylene glycol, tetramethylene glycol, diethylene glycol, polyethylene glycol, polypropylene glycol, Polytetramethylene glycol, hexamethylene glycol, dodecamethylene glycol,
Aliphatic glycols such as neopentyl glycol and alicyclic glycols such as cyclohexane dimethanol 2.2.
Bis (4'-β-hydroxyethoxyphenyl) propane, naphthalene diol, other aromatic di-, etc. can be used.

In the present invention, as the polyester resin, specifically, for example, a thermoplastic polyethylene terephthalate resin produced by polycondensation of terephthalic acid and ethylene glycol, terephthalic acid and tetramethylene can be used. Thermoplastic polybutylene terephthalate resin produced by polycondensation with glycol, terephthalic acid and 1,4
-Thermoplastic polycyclohexane dimethylene terephthalate produced by polycondensation with cyclohexane dimethanol
Resin, thermoplastic polyethylene terephthalate resin produced by copolycondensation of terephthalic acid, isophthalic acid and ethylene glycol, terephthalic acid and ethylene glycol
Thermoplastic polyethylene terephthalate resin produced by copolycondensation of 1,4-cyclohexane dimethanol with terephthalic acid, isophthalic acid, ethylene glycol and propylene glycol A thermoplastic polyethylene terephthalate resin, a polyester polyol resin, or the like can be used. In addition, in the present invention, a saturated aromatic dicarboxylic acid having a benzene nucleus as a basic skeleton as described above, further, for example,
Malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, can also be copolycondensed by adding one or more aliphatic saturated dicarboxylic acids such as dodecanoic acid, It is preferable that about 1 to 10% by weight is added to the aromatic saturated dicarboxylic acid having a benzene nucleus as a basic skeleton. Thus, in the present invention, by using the polyester-based resin as described above, it is possible to improve the close adhesiveness and the like and improve the elongation of the primer layer, for example, laminating, or The purpose of the present invention is to improve suitability for post-processing such as bag-making processing and prevent the occurrence of cracks and the like in the vapor deposition film of inorganic oxide during the post-processing.

Next, in the above, as the silane coupling agent constituting the above resin composition, an organic functional silane monomer having binary reactivity can be used. For example, γ-chloropropyl Trimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyl-tris (β-methoxyethoxy) silane,
γ-methacryloxypropyltrimethoxysilane, β
-(3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, N-β (aminoethyl)-
γ-aminopropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-ureidopropyltriethoxysilane, bis (β-hydroxyethyl) -γ-aminopropyltriethoxysilane, γ- One or more aqueous solutions of aminopropyl silicone can be used.

In the silane coupling agent as described above, a functional group at one end of the molecule, usually a chloro, alkoxy or acetoxy group, is hydrolyzed to form a silanol group (SiOH), which is , A metal constituting the vapor-deposited film of an inorganic oxide, or an active group on the surface of the vapor-deposited film of an inorganic oxide, for example, a functional group such as a hydroxyl group, causes a reaction such as a dehydration condensation reaction by some action. hand,
A silane coupling agent is modified on the surface of the vapor-deposited film of inorganic oxide by a covalent bond, etc., and a strong bond is formed on the surface of the vapor-deposited film of the inorganic oxide of the silanol group itself by adsorption or hydrogen bonding. To do. On the other hand, vinyl at the other end of the silane coupling agent, methacryloxy, amino, epoxy, or an organic functional group such as mercapto is formed on the thin film of the silane coupling agent, for example, an adhesive layer,
Reacts with the substances that make up the other layers to form a strong bond and tightly adheres tightly to enhance its laminate strength,
Thus, in the present invention, it is possible to form a strong laminated structure having high laminate strength. In the present invention, the inorganic and organic properties of the silane coupling agent are utilized to improve the dense adhesion between the vapor-deposited film of an inorganic oxide and the printed pattern layer, the light blocking layer, and other layers. This increases the laminate strength and the like.

Next, in the present invention, as the filler constituting the above resin composition, for example, calcium carbonate,
Barium sulfate, alumina white, silica, talc, glass frit, resin powder, and the like can be used. Thus, the above-mentioned filler adjusts the viscosity and the like of the above-mentioned resin composition liquid, and improves the coating suitability thereof, and at the same time, uses a polyurethane resin or polyester resin as a binder resin and a silane coupling agent. It is bonded via the binding layer to improve the cohesive force of the coating film.

In the present invention, the primer agent layer may be, for example, a polyamide resin or an epoxy resin, in addition to the primer agent layer formed of a coating film of the resin composition described above. , Phenolic resin,
A resin composition containing a (meth) acrylic resin, a polyvinyl acetate resin, a polyolefin resin such as polyethylene aliha polypropylene or a copolymer or modified resin thereof, a cellulose resin, etc. as a vehicle main component It can also be used to form a primer layer. Thus, in the present invention, as in the above, the resin composition described above is used, for example, as a roll coat or a gravure roll coat.
The primer-coating agent layer can be formed by coating using a coating method such as coating, kiss coating, or the like, and the coating amount is 0.1-5.
About g / m ² (dry state) is desirable. However, in the present invention, it is most desirable to use, as the primer agent layer, a primer agent layer made of a resin composition containing the above-mentioned polyurene resin or polyester resin as the main component of the vehicle.

Next, in the present invention, the printed pattern layer constituting the flexible packaging bag according to the present invention will be described.
Examples of such a printed pattern layer include, for example, letters, figures, symbols, patterns, etc. on the primer agent layer provided on the above-mentioned barrier substrate or on the surface substrate film described later. It is possible to form a print pattern layer by printing a desired print pattern including the above. Thus, as the print pattern layer, specifically, first,
It is used as a main component of an ink vehicle composed of one or more kinds of resins and the like, and if necessary, a plasticizer, a stabilizer,
One of additives such as antioxidants, light stabilizers, ultraviolet absorbers, curing agents, cross-linking agents, lubricants, antistatic agents, fillers, etc.
One kind or two or more kinds are arbitrarily added, a coloring agent such as a dye or a pigment is further added, and the mixture is sufficiently kneaded with a solvent, a diluent or the like to prepare an ink composition, and then the ink composition is used. However, for example, using a printing method such as gravure printing, offset printing, letterpress printing, screen printing, transfer printing, flexographic printing, etc., on the primer agent layer provided on the above-mentioned barrier substrate. Alternatively, it is possible to form a printed pattern layer according to the present invention by printing a desired printed pattern consisting of characters, figures, symbols, patterns, etc. on the surface base film described later. .

In the above, the vehicle for ink is a known one, for example, linseed oil, cutting oil, soybean oil,
Hydrocarbon oil, rosin, rosin ester, rosin modified resin, shellac, alkyd resin, phenolic resin,
Maleic acid resin, natural resin, hydrocarbon resin, polyvinyl chloride resin, polyvinyl acetate resin, polystyrene resin, polyvinyl butyral resin, acrylic or methacrylic resin, polyamide resin, polyester resin,
Polyurethane resin, epoxy resin, urea resin, melamine resin, aminoalkyd resin, phenol resin, nitrocellulose, ethyl cellulose, chlorinated rubber,
One or more kinds of cyclized rubber and the like can be used.

Next, in the present invention, the light blocking layer constituting the flexible packaging bag according to the present invention will be described.
As the light blocking layer, first, one kind of resin or two kinds of resin is used.
Mainly consists of at least one kind of vehicle for ink, and if necessary, plasticizer, stabilizer, antioxidant, light stabilizer, UV absorber, curing agent, crosslinking agent, lubricant, antistatic agent, filling One or two or more kinds of additives such as agents and others are optionally added, and further a coloring agent such as a dye or a pigment is added,
A solvent, a diluent, etc. are sufficiently kneaded to prepare an ink composition, and then the ink composition is used, for example, gravure printing, offset printing, letterpress printing, screen printing,
Using a printing method such as transfer printing, flexo printing, etc., on the printed pattern layer provided on the above-mentioned barrier substrate,
Alternatively, on the print pattern layer provided on the surface substrate film described later, by printing a print coating layer consisting of a solid layer,
The light blocking layer according to the present invention can be formed.

Thus, in the present invention, the above-mentioned light-blocking layer blocks the transmission of sunlight or fluorescent light, such as from the sun or fluorescent lamps, and decomposes the contents filled and packaged in the soft packaging bag. Or to prevent photodegradation such as deterioration, fading, and the like. Therefore, in the present invention,
As the print coating layer constituting the above light-shielding layer, a print coating layer made of an ink composition containing a colorant having a property of absorbing, reflecting or diffusing sunlight or the like is desirable. As the colorant having the property of absorbing, reflecting or diffusing the above-mentioned sunlight, specifically, for example, white or black various inorganic or organic dyes, pigments, etc. It is desirable to use a mixture of one or more colorants. In the present invention, the white or black colorant such as various inorganic or organic dyes, pigments and the like,
For example, basic lead carbonate, basic lead sulfate, basic lead silicate, zinc white, zinc sulfide, lithopone, antimony trioxide,
One or more kinds of white pigments such as anatas-type titanium oxide, rutile-type titanium oxide, and the like, or black pigments such as carbon black (channel or furnace) and the like can be used. The amount used is about 0.1 to 30% by weight, preferably 0.5 to 10% by weight, based on the resin that constitutes the vehicle for the ink.
It is desirable to use by adding about wt%.

Further, in the present invention, the above-mentioned light-shielding layer contains a colorant comprising one or more kinds of the above-mentioned white or black various inorganic or organic dyes and pigments. It is desirable that the light blocking layer is composed of two layers, a white printed film layer made of a white ink composition and a black printed film layer made of a black ink composition. Thus, in the present invention, a light-shielding layer composed of two layers, such as the white print coating layer and the black print coating layer described above, allows one layer to absorb sunlight and the other layer. Reflects or diffuses sunlight, etc., and the double action effect of the two layers completely blocks the transmission of sunlight, fluorescence, etc. from the sun or fluorescent lamps, etc. It is intended to enhance the effect of further preventing the photodegradation such as the decomposition or deterioration of the product, or the fading and the like. Furthermore, the white print film layer described above is a base layer of the print pattern layer. It will also have functions, and the characters, figures, symbols, patterns that make up the print pattern layer,
This has the dual advantage that the printed image of other areas can be made even clearer and a beautiful printed pattern can be reproduced or revealed.

In the above, as the vehicle for the ink, which is composed of the resin or the like forming the white ink composition or the black ink composition forming the light-shielding layer, the same as described above can be used.
Known substances such as linseed oil, cutting oil, soybean oil, hydrocarbon oil, rosin, rosin ester, rosin modified resin, shellac, alkyd resin, phenol resin, maleic acid resin, natural resin, hydrocarbon resin , Polyvinyl chloride resin, polyvinyl acetate resin, polystyrene resin, polyvinyl butyral resin, acrylic or methacrylic resin, polyamide resin, polyester resin, polyurethane resin, epoxy resin, urea resin, melamine One or more of resins, aminoalkyd resins, phenol resins, nitrocellulose, ethylcellulose, chlorinated rubber, cyclized rubber and the like can be used.

Next, in the present invention, the heat-sealable resin layer constituting the soft packaging bag according to the present invention will be described. Such heat-sealable resin layers are melted by heat and mutually melted. Any material that can be fused, 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-ethyl acrylate copolymer, ethylene-acrylic acid copolymer, ethylene-
Methacrylic acid copolymer, ethylene-propylene copolymer, methyl pentene polymer, polyolefin resin such as polyethylene or polypropylene with acrylic acid, methacrylic acid, maleic anhydride, fumaric acid, and other unsaturated carboxylic acid A resin film or sheet made of one or more of modified acid-modified polyolefin resin, poly (meth) acrylic resin, polyester resin, polyamide resin, etc. is used. can do.

The above resin film or sheet can be used in a single layer or multiple layers, and the thickness of the above resin film or sheet is 5 μm to 30 μm.
About 0 μm, preferably about 10 μm to 110 μm is desirable. Further, in the present invention, as the thickness of the resin film or sheet described above, as a pouch for a retort pouch, a vapor deposition film of an inorganic oxide constituting a barrier substrate is scratched or cracked. In order to prevent the occurrence of such a phenomenon, it is preferable to make the film thickness relatively thick, specifically, 40 μm to 110 μm, and preferably 50 μm to 100 μm. is there. Therefore, in the present invention, among the above-mentioned resin films or sheets, the thickness of 5 is particularly preferable.
It is preferable to use an unstretched polypropylene film having a size of 0 μm to 100 μm.

Next, in the present invention, the intermediate base material constituting the flexible packaging bag according to the present invention will be described. As the intermediate base material, this is the same as the above-mentioned base material film. Since it is a basic or auxiliary material that constitutes a packaging bag, it has excellent properties in mechanical, physical, chemical, etc., and has excellent strength, as well as heat resistance, moisture resistance, and pinhole resistance. Resistance, puncture resistance,
A resin film or sheet excellent in transparency and the like can be used. Specifically, for example, polyester resin, polyamide resin, polyaramid resin, polypropylene resin, polycarbonate resin,
A film or sheet of a tough resin such as a polyacetal resin, a fluorine resin, or the like can be used. As the resin film or sheet, either an unstretched film or a stretched film uniaxially or biaxially stretched can be used. Further, in the present invention, the thickness of the resin film or sheet may be a thickness that can be kept to the minimum necessary for strength, puncture resistance, rigidity, etc. However, if it is too thin, strength, puncture resistance, and
It is not preferable because the rigidity and the like decrease. In the present invention, for the reasons as described above, about 10 μm to 100 μm, preferably about 12 μm to 50 μm.
The μm level is most desirable. Thus, in the present invention, it is preferable to use a biaxially stretched polyamide resin film having a thickness of about 15 μm to 30 μm among the above-mentioned resin films or sheets.

Next, in the present invention, the surface base material film constituting the flexible packaging bag according to the present invention will be described. As the surface base material film, this is the same as the above-mentioned base material film or intermediate base material. Since it is a basic or auxiliary material constituting the flexible packaging bag according to the present invention, it has excellent properties in mechanical, physical, chemical, etc., and has excellent strength and heat resistance. Resistance, moisture resistance, pinhole resistance, puncture resistance, transparency,
It is possible to use a resin film or sheet excellent in other properties. Specifically, for example, a film of a tough resin such as polyester resin, polyamide resin, polyaramid resin, polypropylene resin, polycarbonate resin, polyacetal resin, fluorine resin, etc. Sheets can be used. Therefore,
As the resin film or sheet, any of unstretched film or stretched film uniaxially or biaxially stretched can be used. Further, in the present invention, the thickness of the resin film or sheet may be a thickness that can be kept to the minimum necessary for strength, puncture resistance, rigidity, etc. There is also a drawback of rising
On the other hand, if it is too thin, strength, puncture resistance, rigidity, etc. are deteriorated, which is not preferable. In the present invention, for the above reasons, it is about 10 μm to 100 μm.
Most preferred is the m-position, preferably about 12 μm to 50 μm. Thus, in the present invention, among the above-mentioned resin films or sheets, particularly, the thickness is 15 μm.
It is preferable to use a biaxially stretched polyamide resin film of m to 30 μm.

By the way, since the packaging bag is usually subjected to severe physical and chemical conditions, strict packaging suitability is required for the laminated material constituting the packaging bag, and the deformation preventing strength is high. , Drop impact strength, pinhole resistance, heat resistance, sealability, quality maintenance, workability, hygiene, etc. are required. Therefore, in the present invention, as described above, In addition to the materials, other materials satisfying the above conditions can be arbitrarily 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, methylpentene polymer, polybutene-based resin, polyvinyl chloride-based resin, polyvinyl acetate-based resin, polyvinylidene chloride-based resin, vinyl chloride-vinylidene chloride copolymer, poly (meta ) Acrylic resin, polyacrylonitrile resin, polystyrene resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), polyester resin, polyamide resin, polycarbonate -Bonnet tree , Polyvinyl alcohol resin, saponified product of ethylene-vinyl acetate copolymer, fluorine resin, diene resin, polyacetal resin, polyurethane resin, nitrocellulose, and other known resin films or the like The sheet can be arbitrarily selected and used. Besides, for example, synthetic paper or the like can also be 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 particular, in the present invention, other base materials include, for example, low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene having a barrier property to prevent permeation of water vapor, water, etc. A film or sheet of a resin such as polypropylene or ethylene-propylene copolymer, or the like can be used. These materials can be used alone or in combination of two or more. The thickness of the above-mentioned film or sheet is arbitrary, but is usually about 5 μm to 300 μm, and more preferably 10 μm to 100 μm.
Rank is desirable.

Next, in the above-mentioned present invention, a method for producing a laminated material constituting the soft packaging bag according to the present invention by using the above-mentioned materials will be explained. Laminating methods used in the production of, for example, wet lamination method, dry lamination method, solventless lamination method, melt extrusion lamination method, melt coextrusion lamination method, inflation method.
Method, coextrusion inflation method, and other methods. Thus, in the present invention, when performing the above-mentioned lamination, if necessary, for example, a pretreatment such as corona treatment, ozone treatment, or frame treatment is optionally performed on the surface of the substrate to be laminated. be able to. Further, in the above, when extrusion laminating, for example, low density polyethylene, medium density polyethylene, high density polyethylene, linear (linear) low density polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ionomer resin , Ethylene-ethyl acrylate copolymer, ethylene-
Acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-propylene copolymer, methylpentene polymer-, polyolefin resin such as polyethylene or polypropylene acrylic acid, methacrylic acid, maleic anhydride, fumaric acid, Acid-modified polyolefin resins modified with unsaturated carboxylic acids such as others can be used as the resin for melt extrusion lamination. At that time, as an adhesion aid, for example, an isocyanate-based, polyethyleneimine-based, or other anchor-coating agent can be optionally used. Further, in the present invention, when dry laminating, for example, vinyl type, acrylic type, polyurethane type, polyamide type, polyester type,
It is possible to use solvent-based, water-based, emulsion-type, other adhesives for laminate, etc., whose main component is a vehicle such as epoxy type.

Next, in the present invention, the soft packaging bag according to the present invention, which is manufactured by making a bag by using the above-mentioned laminated material, will be explained. Such a soft packaging bag uses the above-mentioned laminated material. The surfaces of the heat-sealable resin layers are overlapped with each other so as to face each other, and then the peripheral end portion is heat-sealed to form a seal portion, and an opening portion is provided at the upper end portion. The bag-shaped container body can be manufactured by making a bag. As a bag-making method, the laminated materials as described above are folded or overlapped, the surfaces of the inner layers are made to face each other, and the peripheral end portions thereof are, for example, a side seal type, two One-way seal type, three-way seal type, four-way seal type, envelope-sealed seal type,
Hail depending on the heat seal type such as a seal-sealed seal type (pyro-seal type), pleated seal type, flat bottom seal type, square bottom seal type, gusset type, etc. The soft packaging bag according to the present invention can be manufactured by making a bag and making a bag-shaped container body having various shapes and having an opening at the upper end thereof. In addition, as the soft packaging bag according to the present invention, for example, a self-supporting packaging bag (standing pouch) or the like, or a bag for refilling a synthetic detergent or the like can be used. In the above, as a method of heat seal,
For example, bar seals, rotary roll seals, belt seals
It can be carried out by a known method such as a reel, an impulse seal, a high frequency seal, and an ultrasonic seal.

Next, in the present invention, a description will be given of a packaged product in which the soft packaging bag according to the present invention is used and the contents are filled and packaged therein. First, in the present invention, an opening is formed at the upper end portion produced above. The soft packaging according to the present invention is prepared by filling the contents from the opening of the flexible packaging bag according to the present invention having a portion and then sealing the end of the opening at the upper end with a heat seal or the like. It is possible to manufacture a packaged product using a bag. In the above, as the contents to be filled and packaged in the flexible packaging bag according to the present invention, for example, food and drink, fruit juice, juice, drinking water, sake, cooked food,
Seafood paste, frozen food, meat products, stewed foods, rice cakes, liquid soot
Examples include various foods and drinks such as foods, seasonings and the like, liquid detergents, cosmetics, chemical products, and other articles.

[0051]

EXAMPLES Next, the present invention will be described more specifically by way of examples of the present invention. 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
Oxygen / argon mixed gas plasma treatment was performed at × 10 ⁻⁵ Torr to adjust the surface tension of the deposited surface of silicon oxide to 54 dy.
A plasma-treated surface having an improved ne / cm or more was formed. Further, on the plasma-treated surface formed above, an epoxy-based silane coupling agent (8.0% by weight) and an antiblocking agent (1.
0% by weight) and sufficiently kneaded to obtain a polyurethane resin composition, which is coated by a gravure roll coat method so as to have a film thickness of 0.5 g / m ² (dry state). The barrier substrate was manufactured by coating and then drying to form a primer layer. (2). Next, after using the usual gravure ink composition to form a desired printed pattern by the gravure printing method on the surface of the primer layer of the barrier substrate produced in (1) above, the printed pattern is formed. The following white ink composition and black ink composition are used on the entire surface including the gravure roll
Printing using a printing method and coating each to a thickness of 2.0 g / m ² (dry state) to form a light-shielding layer consisting of two printing coating layers, a white printing coating and a black printing coating. Formed.
Then, on the surface of the light-shielding layer formed above, a two-component curing type adhesive for polyurethane laminate was applied by a gravure roll coat method to a thickness of 4.0 g / m ² (dry state). To
To form a laminate adhesive layer, and then
A biaxially stretched nylon 6 film having a thickness of 15 μm was laminated on the surface of the adhesive layer for laminate with its corona treated surfaces facing each other, and then both layers were dry laminated to be laminated. Furthermore, the biaxially stretched nylon 6 laminated above
On the surface of the film, after subjected to corona discharge treatment, on the corona-treated surface, in the same manner as above, to form a laminate adhesive layer, and thereafter, to the laminate adhesive layer surface, A low-density polyethylene film having a thickness of 100 μm was dry-laminated and laminated to produce a laminated material. (White ink composition) Polyurethane resin 20 parts by weight Titanium oxide 14 parts by weight Solvent ( mixed solvent consisting of ethyl acetate, toluene and isopropyl alcohol ) 66 parts by weight Total 100 parts by weight (black ink composition) Polyurethane resin 22 parts by weight Parts carbon black 12 parts by weight solvent ( mixed solvent consisting of ethyl acetate, toluene, isopropyl alcohol ) 66 parts by weight total 100 parts by weight (3). Next, two sheets of the laminated material produced above are prepared, and the surfaces of the low-density polyethylene films are overlapped so as to face each other, and then the ends around the outer periphery are three-way heat-sealed to seal. A three-way seal type flexible packaging bag having a portion formed with an opening at the top was manufactured. In the three-way seal type soft packaging bag produced above, the dressing is filled and packaged through the opening, and then the end of the opening is heat-sealed to form the upper seal. Formed to produce a packaged product. The packaging product produced above has a packaging bag having strength and the like, and has weather resistance, heat resistance, water resistance, heat seal resistance, pinhole resistance, puncture resistance, and the like. It has excellent physical properties, in particular, it has excellent barrier properties that prevent the permeation of oxygen gas, water vapor, etc., and it also has excellent light blocking properties. It has excellent suitability for filling and packaging of contents, suitability for distribution, storage suitability, etc. Moreover, it does not generate harmful substances when incinerated and disposed of after use, and is suitable for disposal.
It was extremely excellent in environmental suitability.

Example 2 (1). As the base film, a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm is used.
The above-mentioned biaxially stretched polyethylene terephthalate film was mounted on a delivery roll of a winding 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: 420 m / min Deposition surface : Corona treated surface Next, immediately after the vapor deposition film of aluminum oxide having a thickness of 200Å was formed above, a glow discharge plasma generator was used on the vapor deposition film surface of aluminum oxide, and a power of 9k was used.
w, oxygen gas (O ₂ ): Argon gas (Ar) = 7.
A mixed gas of 0: 2.5 (unit: slm) was used, and oxygen / argon mixed gas plasma treatment was performed at a mixed gas pressure of 6 × 10 ⁻⁵ Torr to form a plasma treated surface. Next, on the plasma-treated surface of the aluminum oxide vapor-deposited film formed above, an initial condensation product of a polyurethane resin, an epoxy silane coupling agent (8.0% by weight) and an antiblocking agent (1.0 Wt%),
A primer-resin composition prepared by sufficiently kneading was used, and a film thickness of 0.5 g / m 2 was obtained by a gravure roll-coat method.
^By coating so as to be ² (dry state), a primer layer was formed to produce a barrier substrate. (2). Next, after using the usual gravure ink composition to form a desired printed pattern by the gravure printing method on the surface of the primer layer of the barrier substrate produced in (1) above, the printed pattern is formed. The same white ink composition and black ink composition as the white ink composition and the black ink composition used in the above-mentioned Example 1 were similarly used on the entire surface including
1. Printed using the gravure roll coat method, each having a thickness of 2.
The coating was applied to 0 g / m ² (dry state) to form a light blocking layer composed of two print coating layers, a white print coating and a black print coating. Then, on the surface of the light-shielding layer formed as described above, a two-component curing type polyurethane adhesive for laminating was applied by a gravure roll coat method to a thickness of 4.0 g / m ^2.
The adhesive layer for laminate is formed by coating in a (dry state), and then a biaxially stretched nylon 6 film having a thickness of 15 μm is formed on the corona-treated surface of the adhesive layer for laminate. The layers were placed facing each other, and then both layers were dry-laminated and laminated. Further, the surface of the biaxially stretched nylon 6 film laminated as described above is subjected to corona discharge treatment, and then the adhesive layer for laminate is formed on the corona-treated surface in the same manner as described above. A low-density polyethylene film having a thickness of 100 μm was dry-laminated and laminated on the surface of the adhesive layer for laminating to produce a laminated material. (3). Next, two sheets of the laminated material produced above are prepared, and the surfaces of the low-density polyethylene films are overlapped so as to face each other, and then the ends around the outer periphery are three-way heat-sealed to seal. A three-way seal type flexible packaging bag having a portion formed with an opening at the top was manufactured. In the three-way seal type soft packaging bag produced above, the dressing is filled and packaged through the opening, and then the end of the opening is heat-sealed to form the upper seal. Formed to produce a packaged product. The packaging product produced above has a packaging bag having strength and the like, and has weather resistance, heat resistance, water resistance, heat seal resistance, pinhole resistance, puncture resistance, and the like. It has excellent physical properties, in particular, it has excellent barrier properties that prevent the permeation of oxygen gas, water vapor, etc., and it also has excellent light blocking properties. It has excellent suitability for filling and packaging of contents, suitability for distribution, storage suitability, etc. Moreover, it does not generate harmful substances when incinerated and disposed of after use, and is suitable for disposal.
It was extremely excellent in environmental suitability.

Example 3 (1). Biaxial stretching with a thickness of 15 μm as a base film
Nylon 6 film is used and this is plasma chemical vapor phase
Attached to the delivery roll of the growth device, and set the thickness under the following conditions.
A 150 Å silicon oxide vapor-deposited film is applied to the above biaxially stretched nylon 6
It was formed on one side of the film. (Deposition conditions) Reaction gas mixture ratio: Hexamethyldisiloxane: Oxygen gas
Space: Helium = 1:11:10 (Unit: slm) Degree of vacuum in the vacuum chamber: 5.2 × 10^-6mbar Degree of vacuum in vapor deposition chamber: 5.1 × 10^-2mbar Cooling / electrode drum power supply: 18kW Film transport speed: 70 m / min Deposition surface: Corona treated surface Next, the biaxially stretched nitriding film on which the vapor-deposited film of silicon oxide is formed as described above.
On the surface of the deposited silicon oxide film of Ron 6 film, the glow discharge
Using a plasma generator, power-9kw, oxygen gas (O
₂): Argon gas (Ar) = 7.0: 2.5 (unit:
slm) and a mixed gas pressure of 6 × 1
0^-FiveOxygen / argon mixed gas plasma treatment with Torr
Performed to form a plasma treated surface. Then formed above
The surface of the vapor-deposited silicon oxide film subjected to plasma treatment was coated with polyurea.
Epoxy-based silane cup on the initial condensation product of tan resin
Ring agent (8.0% by weight) and antiblocking agent (1.
0% by weight) and kneaded sufficiently to form a primer tree
A fat composition is used, which is subjected to the gravure roll coat method.
, Film thickness 0.5g / m ²To make it (dry)
To form a primer layer, and a barrier substrate
Manufactured. (2). On the other hand, as the surface base film, the thickness is 12 μm
Uses biaxially stretched polyethylene terephthalate film
The normal gravure ink set on the corona treated surface.
Using the product, shape the desired print pattern using the gravure printing method.
After being formed, the above-mentioned Example 1 is applied to the entire surface including the printed pattern.
The white ink composition and the black ink composition used in
Use the same white ink composition and black ink composition in the same way.
And print using the gravure roll coat method.
2.0 g / m²Coat (dry) and white
It consists of two layers of printing film, a color printing film and a black printing film.
A light blocking layer was formed. Next, the light blocking property formed above
Two-component curing type polyurethane laminate contact on the layer surface
A gravure roll coat method was used for the binder to give a thickness of 4.0 g /
m²Adhesion for lamination by coating in (dry state)
An adhesive layer is formed, and then, on the adhesive layer surface for laminating,
Primer agent layer of barrier substrate produced in the above (1)
The two surfaces were opposed to each other, and both layers were dry-laminated.
Furthermore, a dry laminated base material is constructed.
15μm thick biaxially stretched nylon 6 film surface
, After the corona discharge treatment, on the corona treated surface,
In the same manner as above, an adhesive layer for laminate is formed, and
After curing, a thickness of 100 is applied to the surface of the adhesive layer for laminating.
Dry lamination of low-density polyethylene film of μm
And laminated to produce a laminated material. (3). Next, prepare 2 sheets of laminated material manufactured above
Then, place the low-density polyethylene film facing the
After aligning, and then the edges around the perimeter are three-way heat
Seal to form a seal part and have an opening above.
A three-way seal type flexible packaging bag was manufactured. Manufactured above
In the three-way seal type flexible packaging bag,
Fill and wrap the Lessing, then the end of its opening
Heat seal to form the upper seal and
Manufactured. The packaging product manufactured above is the packaging bag.
However, it has strength, weather resistance, heat resistance, water resistance and heat resistance.
-Toilet resistance, pinhole resistance, puncture resistance, etc.
It has excellent physical properties, such as oxygen gas and water vapor.
It has excellent barrier properties to prevent light and light blocking properties
Function as a container for use, such as bag breakage or leakage of contents
Etc. are not recognized, and the suitability for filling and packaging of contents, proper distribution,
It has excellent suitability, and it is incinerated and disposed of after use.
Suitability for disposal without the generation of harmful substances, etc.
It was extremely excellent in environmental suitability.

Example 4 Instead of using a low-density polyethylene film having a thickness of 100 μm as the heat-sealable resin layer in Example 1 above, an unstretched polypropylene film having a thickness of 100 μm was used. Except for the above, the same result as in Example 1 was obtained.

Example 5 Instead of using a low-density polyethylene film having a thickness of 100 μm as the heat-sealable resin layer in Example 2 above, an unstretched polypropylene film having a thickness of 100 μm was used. Except for the above, the same result as in Example 2 was obtained.

Example 6 Instead of using a 100 μm thick low density polyethylene film as the heat-sealable resin layer in Example 3 above, a 100 μm thick unstretched polypropylene film was used. The same results were obtained as in Example 3 except for the above.

Example 7 (1). As the base film, a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm is used.
The above-mentioned biaxially stretched polyethylene terephthalate film was mounted on a delivery roll of a winding type vacuum vapor deposition device, and then it was fed out, and the corona-treated surface of the biaxially stretched polyethylene terephthalate film was placed on the aluminum. Was used as a vapor deposition source, and a vapor deposition film of aluminum oxide having a film thickness of 200 Å was formed under the following vapor deposition conditions by a vacuum vapor deposition method using an electron beam (EB) heating system while supplying oxygen gas. (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: 420 m / min Deposition surface : Corona treated surface Next, immediately after the vapor deposition film of aluminum oxide having a thickness of 200Å was formed above, a glow discharge plasma generator was used on the vapor deposition film surface of aluminum oxide, and a power of 9k was used.
w, oxygen gas (O ₂ ): Argon gas (Ar) = 7.
A mixed gas of 0: 2.5 (unit: slm) was used, and oxygen / argon mixed gas plasma treatment was performed at a mixed gas pressure of 6 × 10 ⁻⁵ Torr to form a plasma treated surface. Next, on the plasma-treated surface of the aluminum oxide vapor-deposited film formed above, an initial condensation product of a polyurethane resin, an epoxy silane coupling agent (8.0% by weight) and an antiblocking agent (1.0 Wt%),
A primer-resin composition prepared by sufficiently kneading was used, and a film thickness of 0.5 g / m 2 was obtained by a gravure roll-coat method.
^By coating so as to be ² (dry state), a primer layer was formed to produce a barrier substrate. (2). Next, after using the usual gravure ink composition to form a desired printed pattern by the gravure printing method on the surface of the primer layer of the barrier substrate produced in (1) above, the printed pattern is formed. The same white ink composition and black ink composition as the white ink composition and the black ink composition used in the above-mentioned Example 1 were similarly used on the entire surface including
1. Printed using the gravure roll coat method, each having a thickness of 2.
The coating was applied to 0 g / m ² (dry state) to form a light blocking layer composed of two print coating layers, a white print coating and a black print coating. Then, on the surface of the light-shielding layer formed above, a two-component curing type adhesive for polyurethane laminate was applied by a gravure roll coat method to a thickness of 4.0 g / m 2.
² (dry state) to form an adhesive layer for laminating, and then an unstretched polypropylene film having a thickness of 100 μm is laminated on the adhesive layer for laminating by dry laminating. To produce a laminated material. (3). Next, two sheets of the laminated material produced as described above are prepared, and the surfaces of the unstretched polypropylene films are laminated so as to face each other, and thereafter, the end portions around the outer periphery thereof are three-sided.
A three-way seal type soft packaging bag having a seal portion formed by tossing and having an opening portion above was manufactured. In the three-way seal type soft packaging bag produced above, the dressing is filled and packaged through the opening, and then the end of the opening is heat-sealed to form the upper seal. Formed to produce a packaged product. The packaging product produced above has a packaging bag having strength and the like, and has weather resistance, heat resistance, water resistance, heat seal resistance, pinhole resistance, puncture resistance, and the like. It has excellent physical properties, in particular, it has excellent barrier properties that prevent the permeation of oxygen gas, water vapor, etc., and it also has excellent light blocking properties. It has excellent suitability for filling and packaging of contents, suitability for distribution, storage suitability, etc. Moreover, it does not generate harmful substances when incinerated and disposed of after use, and is suitable for disposal.
It was extremely excellent in environmental suitability.

Example 8 (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
Oxygen / argon mixed gas plasma treatment was performed at × 10 ⁻⁵ Torr to adjust the surface tension of the deposited surface of silicon oxide to 54 dy.
A plasma-treated surface having an improved ne / cm or more was formed. Further, on the plasma-treated surface formed above, an epoxy-based silane coupling agent (8.0% by weight) and an antiblocking agent (1.
0% by weight) and sufficiently kneaded to obtain a polyurethane resin composition, which is coated by a gravure roll coat method so as to have a film thickness of 0.5 g / m ² (dry state). The barrier substrate was manufactured by coating and then drying to form a primer layer. (2). Next, after using the usual gravure ink composition to form a desired printed pattern by the gravure printing method on the surface of the primer layer of the barrier substrate produced in (1) above, the printed pattern is formed. The same white ink composition and black ink composition as the white ink composition and the black ink composition used in the above-mentioned Example 1 were similarly used on the entire surface including
1. Printed using the gravure roll coat method, each having a thickness of 2.
The coating was applied to 0 g / m ² (dry state) to form a light blocking layer composed of two print coating layers, a white print coating and a black print coating. Then, on the surface of the light-shielding layer formed above, a two-component curing type adhesive for polyurethane laminate was applied by a gravure roll coat method to a thickness of 4.0 g / m 2.
² (dry state) to form an adhesive layer for laminating, and then an unstretched polypropylene film having a thickness of 100 μm is laminated on the adhesive layer for laminating by dry laminating. To produce a laminated material. (3). Next, two sheets of the laminated material produced as described above are prepared, and the surfaces of the unstretched polypropylene films are laminated so as to face each other, and thereafter, the end portions around the outer periphery thereof are three-sided.
A three-way seal type soft packaging bag having a seal portion formed by tossing and having an opening portion above was manufactured. In the three-way seal type soft packaging bag produced above, the dressing is filled and packaged through the opening, and then the end of the opening is heat-sealed to form the upper seal. Formed to produce a packaged product. The packaging product produced above has a packaging bag having strength and the like, and has weather resistance, heat resistance, water resistance, heat seal resistance, pinhole resistance, puncture resistance, and the like. It has excellent physical properties, in particular, it has excellent barrier properties that prevent the permeation of oxygen gas, water vapor, etc., and it also has excellent light blocking properties. It has excellent suitability for filling and packaging of contents, suitability for distribution, storage suitability, etc. Moreover, it does not generate harmful substances when incinerated and disposed of after use, and is suitable for disposal.
It was extremely excellent in environmental suitability.

Comparative Example 1 (1). An ordinary gravure ink composition was used on the corona-treated surface of a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm to form a desired printed pattern by a gravure printing method, and then the entire surface including the printed pattern was coated with 2 A liquid-curable polyurethane adhesive for laminate was coated to a thickness of 4.0 g / m ² (dry state) using a gravure roll coat method to form an adhesive layer for laminate. Then, a biaxially stretched nylon 6 film having a thickness of 15 μm was dry laminated and laminated on the adhesive layer surface for laminating. Next, the surface of the laminated biaxially stretched nylon 6 film having a thickness of 15 μm is subjected to corona discharge treatment, and then the adhesive layer for laminate is formed on the corona-treated surface in the same manner as above. Then, dry laminating a 7 μm thick aluminum foil on the surface of the laminating adhesive layer.
And laminating, and further, on the surface of the aluminum foil laminated above, in the same manner as above, to form an adhesive layer for laminating, and thereafter, on the adhesive layer surface for laminating, a thickness of A low-density polyethylene film having a thickness of 100 μm was dry-laminated and laminated to produce a laminated material. (2). Next, two sheets of the laminated material produced above are prepared, and the surfaces of the low-density polyethylene films are overlapped so as to face each other, and then the ends around the outer periphery are three-way heat-sealed to seal. A three-way seal type flexible packaging bag having a portion formed with an opening at the top was manufactured. In the three-way seal type soft packaging bag produced above, the dressing is filled and packaged through the opening, and then the end of the opening is heat-sealed to form the upper seal. Formed to produce a packaged product.

Comparative Example 2 (1). An ordinary gravure ink composition was used on the corona-treated surface of a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm to form a desired printed pattern by a gravure printing method, and then the entire surface including the printed pattern was coated with 2 A liquid-curable polyurethane adhesive for laminate was coated to a thickness of 4.0 g / m ² (dry state) using a gravure roll coat method to form an adhesive layer for laminate. Then, a 15 μm-thick biaxially stretched nylon 6 film having an aluminum vapor deposition film having a thickness of 400 Å is made to face the adhesive layer layer for laminate with the surface of the aluminum vapor deposition film facing outward, Both were dry laminated and laminated. Next, biaxially stretched nylon 6 having a thickness of 15 μm and having the aluminum vapor-deposited film having a thickness of 400 Å laminated as described above.
On the surface of the corona-treated surface of the film (after corona discharge treatment, on the corona-treated surface), an adhesive layer for laminate is formed in the same manner as above, and thereafter, the laminate described above is formed. A low-density polyethylene film having a thickness of 100 μm was dry-laminated and laminated on the adhesive layer surface for use as a laminated material. (2). Next, two sheets of the laminated material produced above are prepared, and the surfaces of the low-density polyethylene films are overlapped so as to face each other, and then the ends around the outer periphery are three-way heat-sealed to seal. A three-way seal type flexible packaging bag having a portion formed with an opening at the top was manufactured. In the three-way seal type soft packaging bag produced above, the dressing is filled and packaged through the opening, and then the end of the opening is heat-sealed to form the upper seal. Formed to produce a packaged product.

Comparative Example 3 (1). An ordinary gravure ink composition was used on the corona-treated surface of a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm to form a desired printed pattern by a gravure printing method, and then the entire surface including the printed pattern was coated with 2 A liquid-curable polyurethane adhesive for laminate was coated to a thickness of 4.0 g / m ² (dry state) using a gravure roll coat method to form an adhesive layer for laminate. Then, a 15 μm thick saponified film of an ethylene-vinyl acetate copolymer was dry-laminated and laminated on the adhesive layer surface for lamination. Next, the thickness 1 laminated above
On the surface of the saponified film of the ethylene-vinyl acetate copolymer having a thickness of 5 μm, an adhesive layer for laminate is formed in the same manner as described above, and thereafter, a thickness of the adhesive layer for laminate is formed. A 15 μm biaxially stretched nylon 6 film was dry laminated and laminated, and further, the above laminated thickness 1
An adhesive layer for laminate is formed on the surface of the biaxially stretched nylon 6 film having a thickness of 5 μm in the same manner as above, and thereafter,
A low-density polyethylene film having a thickness of 100 μm was dry-laminated and laminated on the surface of the adhesive layer for lamination to produce a laminated material. (2). Next, two sheets of the laminated material produced above are prepared, and the surfaces of the low-density polyethylene films are overlapped so as to face each other, and then the ends around the outer periphery are three-way heat-sealed to seal. A three-way seal type flexible packaging bag having a portion formed with an opening at the top was manufactured. In the three-way seal type soft packaging bag produced above, the dressing is filled and packaged through the opening, and then the end of the opening is heat-sealed to form the upper seal. Formed to produce a packaged product.

Comparative Example 4 (1). An ordinary gravure ink composition was used on the corona-treated surface of a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm to form a desired printed pattern by a gravure printing method, and then the entire surface including the printed pattern was coated with 2 A liquid-curable polyurethane adhesive for laminate was coated to a thickness of 4.0 g / m ² (dry state) using a gravure roll coat method to form an adhesive layer for laminate. Then, a biaxially stretched nylon 6 film having a thickness of 15 μm was dry laminated and laminated on the adhesive layer surface for laminating. Next, the surface of the laminated biaxially stretched nylon 6 film having a thickness of 15 μm is subjected to corona discharge treatment, and then the adhesive layer for laminate is formed on the corona-treated surface in the same manner as above. Then, dry laminating a 7 μm thick aluminum foil on the surface of the laminating adhesive layer.
And laminating, and further, on the surface of the aluminum foil laminated above, in the same manner as above, to form a laminate adhesive layer, and thereafter, on the laminate adhesive layer surface, a thickness A 100 μm thick unstretched polypropylene film was dry laminated and laminated to produce a laminated material. (2). Next, two sheets of the laminated material produced as described above are prepared, and the surfaces of the unstretched polypropylene films are laminated so as to face each other, and thereafter, the end portions around the outer periphery thereof are three-sided.
A three-way seal type soft packaging bag having a seal portion formed by tossing and having an opening portion above was manufactured. In the three-way seal type soft packaging bag produced above, the dressing is filled and packaged through the opening, and then the end of the opening is heat-sealed to form the upper seal. Formed to produce a packaged product.

Comparative Example 5 (1). An ordinary gravure ink composition was used on the corona-treated surface of a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm to form a desired printed pattern by a gravure printing method, and then the entire surface including the printed pattern was coated with 2 A liquid-curable polyurethane adhesive for laminate was coated to a thickness of 4.0 g / m ² (dry state) using a gravure roll coat method to form an adhesive layer for laminate. Then, a 15 μm thick saponified film of an ethylene-vinyl acetate copolymer was dry-laminated and laminated on the adhesive layer surface for lamination. Next, the thickness 1 laminated above
On the surface of the saponified film of the ethylene-vinyl acetate copolymer having a thickness of 5 μm, an adhesive layer for laminate is formed in the same manner as described above, and thereafter, a thickness of the adhesive layer for laminate is formed. A 15 μm biaxially stretched nylon 6 film was dry laminated and laminated, and further, the above laminated thickness 1
An adhesive layer for laminate is formed on the surface of the biaxially stretched nylon 6 film having a thickness of 5 μm in the same manner as above, and thereafter,
An unstretched polypropylene film having a thickness of 100 μm was dry-laminated and laminated on the surface of the adhesive layer for laminating to produce a laminated material. (2). Next, two sheets of the laminated material produced as described above are prepared, and the surfaces of the unstretched polypropylene films are laminated so as to face each other, and thereafter, the end portions around the outer periphery thereof are three-sided.
A three-way seal type soft packaging bag having a seal portion formed by tossing and having an opening portion above was manufactured. In the three-way seal type soft packaging bag produced above, the dressing is filled and packaged through the opening, and then the end of the opening is heat-sealed to form the upper seal. Formed to produce a packaged product.

Experimental Example The laminated materials produced in Examples 1 to 8 and Comparative Examples 1 to 5 and the flexible packaging bags produced by using the laminated materials were evaluated for the following evaluation items. (1). Measurement of light-shielding property This is a model name, SM color computer manufactured by Suga Test Instruments Co., Ltd. for the laminated materials constituting the flexible packaging bags manufactured in Examples 1 to 8 and Comparative Examples 1 to 5 above. The total light transmittance was measured with a terminating tool and evaluated. (2). Measurement of oxygen permeability This is a temperature of 23 ° C. and a humidity of 90 for the laminated materials produced in the above Examples 1 to 8 and Comparative Examples 1 to 5.
The measurement was carried out under the condition of% RH using a measuring machine (model name, OXTRAN) manufactured by MOCON, USA. (3). Measurement of water vapor permeability This is a temperature of 40 ° C. and a humidity of 90 for the laminated materials produced in the above Examples 1 to 8 and Comparative Examples 1 to 5.
A measuring instrument manufactured by Mocon, Inc. (model name, Permatran) under the condition of% RH.
It was measured at. (4). Measurement of Pinhole This is 3 for the soft packaging bags produced in the above Examples 1 to 8 and Comparative Examples 1 to 5 using the Gelbo tester.
The measurement was performed 2000 times, and the number of pinholes was counted and measured for the laminated material constituting the flexible packaging bag. (5). Measurement of Functionality This is the dressing in which the soft packaging bags produced in the above Examples 1 to 8 and Comparative Examples 1 to 5 are filled and packaged and stored in an oven at 40 ° C. for 1 day, and then , The bag was opened, and the presence or absence of odor was confirmed by 5 testers and measured.
Indicates almost no odor, ○ indicates a slight odor, Δ indicates a odor, ×
Represents a pretty odor. The above measurement results are shown in Table 1 below.

[0065] In Table 1 above, the unit of oxygen permeability is [cc / m
² / day 23 ° C ・ 90% RH], and the unit of water vapor permeability is [g / m ² / day ・ 40 ° C ・ 90% RH]
H], and the number of pinholes is number / A4 size.

As is clear from the measurement results shown in Table 1 above, the samples according to Examples 1 to 8 are sufficiently practical in terms of light blocking property, oxygen permeability and water vapor permeability. It was confirmed, and it was also excellent in pinhole resistance, aroma retention and the like. On the other hand, those according to Comparative Examples 1, 2 and 4 are excellent in light blocking property, oxygen permeability and water vapor permeability, and are also excellent in pinhole resistance, aroma retention, etc. The pinhole properties are slightly poor, and those of Comparative Examples 3 and 5 have oxygen permeability, water vapor permeability, and pinhole resistance.
Although it is excellent in the light blocking property,
In addition, the fragrance retaining property was not sufficiently satisfactory.

[0067]

As is apparent from the above description, according to the present invention, first, an inorganic oxide such as aluminum oxide or silicon oxide is vapor-deposited on one surface of a base film made of the above resin film or the like. A membrane is also provided to produce a barrier substrate,
Then, aluminum oxide constituting the barrier substrate,
After the surface of the deposited film of an inorganic oxide such as silicon oxide is subjected to a pretreatment such as corona discharge treatment or plasma treatment, a primer agent containing a polyurethane resin or a polyester resin as a main component of the vehicle, for example. And then a desired printed pattern layer is provided on the primer agent layer, and then a white printed film layer of a white ink composition is formed on the entire surface including the printed pattern layer. A light blocking layer composed of two layers of a black ink coating layer and a black ink coating layer is provided, and the white printing film layer constituting the above light blocking layer also serves as a base layer for the above printed pattern layer. Then, a heat-sealable resin layer is laminated on the above black printed film layer to produce a laminated material as a packaging material, and then the laminated material is used and produced. Bags to produce flexible packaging bags, and then Manufactures packaging products with filling and packaging contents, such as a desired food and beverage in the soft packaging bag has a strength and the like,
Moreover, it has excellent physical properties such as weather resistance, heat resistance, water resistance, heat seal resistance, pinhole resistance, puncture resistance, etc.,
In particular, it has an excellent barrier property to prevent the permeation of oxygen gas, water vapor, etc. and an excellent light-shielding property. For example, it blocks the permeation of sunlight, fluorescent light, etc. by the sun, fluorescent lamps, etc., and the contents are decomposed or altered. Or, it does not cause photo-degradation such as fading, etc., has suitability for filling and packaging of contents, suitability for storage, etc. Furthermore, it does not generate harmful substances when incinerated and disposed of after use. In addition, it is possible to manufacture a flexible packaging bag having excellent disposal suitability, environmental suitability and the like.

[Brief description of drawings]

FIG. 1 is a schematic cross-sectional view showing a layer structure of an example of a laminated material that constitutes a flexible package according to the present invention.

FIG. 2 is a schematic cross-sectional view showing a layer structure of an example of a laminated material constituting a flexible package according to the present invention.

FIG. 3 is a schematic cross-sectional view showing a layer structure of an example of a laminated material constituting a flexible package according to the present invention.

FIG. 4 is a schematic cross-sectional view showing a layer structure of an example of a laminated material constituting a flexible package according to the present invention.

FIG. 5 is a schematic cross-sectional view showing a layer structure of an example of a laminated material that constitutes a flexible package according to the present invention.

FIG. 6 is a schematic perspective view showing a configuration of a flexible packaging bag according to the present invention, which is manufactured by using the laminated material shown in FIG. 1 and making a bag.

FIG. 7 is a schematic perspective view showing the configuration of a packaged product in which the flexible packaging bag according to the present invention is used and the contents are filled and packaged therein.

FIG. 8 is a schematic configuration diagram showing an outline of an example of a winding type vacuum vapor deposition device.

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

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 Base film 2 Inorganic oxide vapor deposition film 3 Barrier base 4 Light blocking layer 5 Heat sealable resin layer 6 Pretreatment layer 7 Primer layer 8 Print pattern layer 9 Intermediate base 10 Surface base Material Film A, A ₁ , A ₂ Laminated material B Soft packaging bag C Packaging product

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C23C 16/42 C23C 16/42 (72) Inventor Kenji Ageo 1-1-1, Ichigaya-Kagacho, Shinjuku-ku, Tokyo Issue F-Term in Dai Nippon Printing Co., Ltd. (reference) 3E067 AB01 AB81 BB25A CA04 CA06 CA07 CA12 CA17 CA24 EA06 EB01 EB22 FC01 GD07 GD10 3E086 AA23 AC07 AD01 BA04 BA13 BA15 BA33 BA40 BB02 BB05 CA01 CA22 CA22 CA22 CA22 CA01 AA17B AA19B AA20B AK01A AK03D AK46E AR00C AR00D AT00A AT00E BA04 BA05 BA07 BA10A BA10D BA10E EH66B EJ38A EJ38E EJ55 EJ61 GB15 GB23 HB00E HB31C HB31E JB07 JD03 JD04 JJ03 JK01 JK14 JL09 JL10C JL12 JL12D JN02C 4K029 AA11 AA25 BA44 BC00 BD00 GA03 4K030 BA44 CA07 CA12 DA08 LA01 LA11

Claims (12)

[Claims] 1. At least three layers of a barrier substrate having a vapor deposited film of an inorganic oxide on one surface of a substrate film, a light blocking layer, and a heat sealable resin layer, at least. , A barrier substrate having a vapor deposited film of an inorganic oxide on one surface of the substrate film, a light blocking layer, an intermediate substrate, and a heat sheet.
With a transparent resin layer, or at least a surface base material film, a light blocking layer, and a barrier base material having a vapor deposited film of an inorganic oxide on one surface of the base material film, and a heat-resistant layer. Toshi
A flexible packaging bag, which is made by forming a laminated material in which four layers of a flexible resin layer are sequentially laminated. 2. The vapor-deposited film of an inorganic oxide constituting a barrier substrate has a primer agent layer, or a primer agent layer and a printed pattern layer, according to claim 1 above. Flexible packaging bag. 3. The flexible packaging bag according to any one of claims 1 and 2, wherein the surface base film has a printed pattern layer. 4. The flexible packaging bag according to any one of claims 1 to 3, wherein the base film is a biaxially stretched resin film or sheet. 5. The vapor deposition film of inorganic oxide comprises a vapor deposition film of inorganic oxide by physical vapor deposition or chemical vapor deposition, according to any one of claims 1 to 4 above. Soft packaging bag to be described. 6. The flexible packaging bag according to any one of claims 1 to 5, wherein the vapor-deposited film of an inorganic oxide is a vapor-deposited film of aluminum oxide formed by physical vapor deposition. 7. The flexible packaging bag according to any one of claims 1 to 6, wherein the vapor-deposited film of an inorganic oxide is a vapor-deposited film of silicon oxide formed by chemical vapor deposition. 8. The flexible packaging bag according to any one of claims 1 to 7, wherein the light-shielding layer is a printed film layer made of an ink composition. 9. The light-shielding layer is composed of two layers, a white printed film layer made of a white ink composition and a black printed film layer made of a black ink composition, and the white printed film layer is further formed by:
The flexible packaging bag according to any one of claims 1 to 8, which also serves as a base layer of the printed pattern layer. 10. The heat sealable resin layer comprises a polyolefin resin layer, as set forth in claim 1.
The flexible packaging bag according to any one of items 1 to 9. 11. The method according to claim 1, wherein the intermediate base material comprises a biaxially stretched polyamide resin film.
10. The flexible packaging bag described in any one of 10. 12. The flexible packaging bag according to any one of claims 1 to 11, wherein the surface base material film is a biaxially stretched resin film or sheet.