JP2003205570A - Laminate material for packaging liquid seasoning and bag for packaging liquid seasoning using the laminate material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminate material for packaging a liquid seasoning which exhibits superb transparency and high barrier properties and besides, shows excellent aroma retaining properties and superb impact resistance, anti- piercing quality, shelf stability of contents, and further, has advantages such as high suitability for after-processing, reliable lamination strength and good suitability for filling/packaging with a liquid seasoning and the like, and a bag for packaging a liquid seasoning using this laminate material. <P>SOLUTION: This laminate material for packaging the liquid seasoning is of such a structure that a single-layer thin film or a multi-layer thin film of at least two laminate made of an inorganic oxide, are formed on one side of a base material, and a thin coating film formed of an aroma retaining primer composition using a polyester resin as a main component of a vehicle, is formed on the thin film of the inorganic oxide and further that at least a heat-sealing resin layer is laminated on the thin coating film. Besides, the bag for packaging a liquid seasoning obtained by making a box or a bag using the laminate material for packaging a liquid seasoning, is provided. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a liquid seasoning packaging laminated material and a liquid seasoning packaging bag using the same, and more specifically, to transparency, gas barrier properties against oxygen gas, water vapor, and the like. Permeates the contained aroma components,
Excellent in aroma retention, impact resistance, puncture resistance, laminate strength, storage stability for contents, etc. to prevent odor leakage,
Dressing, oil, soy sauce, miso, sauce, vinegar, mayonnaise
TECHNICAL FIELD The present invention relates to a liquid seasoning packaging laminated material useful for filling and packaging liquid seasonings such as bread, noodle soup, soup, etc., and a liquid seasoning packaging bag using the same.

[0002]

2. Description of the Related Art Conventionally, in order to fill and package liquid seasonings and the like, packaging materials of various forms having a predetermined filling and packaging suitability have been developed and proposed. Thus, such a packaging material is, of course, provided with various physical properties such as mechanical, physical, chemical and other properties as a packaging material, but in particular, oxygen gas, water vapor, It has a high gas barrier property (gas barrier property) that prevents the permeation of gas that alters the contents such as others, and also has an aroma-preserving property that prevents the leakage of odors, etc. by permeating the aroma components contained in the contents. Is strongly requested. By the way, in recent years, as a barrier material having a high gas barrier property for blocking oxygen gas or water vapor, for example, a physical vapor deposition method such as a vacuum deposition method, a sputtering method, an ion plating method or the like is formed on the surface of a plastic substrate. (PV
D method) or a chemical vapor deposition method (CV) such as plasma chemical vapor deposition method, thermochemical vapor deposition method, photochemical vapor deposition method, or the like.
Attention has been focused on a gas barrier film obtained by forming a vapor deposition film of an inorganic oxide such as silicon oxide, aluminum oxide, magnesium oxide, etc. using the method D) or the like. In addition, in the above-mentioned gas barrier film, as a plastic substrate, a resin such as a biaxially stretched polyethylene terephthalate film, a nylon film, a biaxially stretched polypropylene film or an ethylene-vinyl alcohol copolymer film is usually used. The film is used. The gas barrier film proposed above is optionally laminated with other plastic film, other base material, etc. to produce a packaging laminate material having various forms, for example, liquid seasoning or its processing. It is expected to be useful as a packaging material for filling and packaging products and the like.

[0003]

However, the above-mentioned gas barrier film is produced by bag-making using a packaging laminated material obtained by optionally laminating other plastic film, other base material and the like. In a packaged product in which the liquid seasoning or the like is filled in the packed packaging bag, oxygen gas,
Regarding the gas barrier property of preventing the permeation of gas, such as water vapor, which alters the contents, it is hard to say that it is sufficiently satisfactory, but it has some effects, and Therefore, the fragrance-preserving property of permeating the aroma components contained in the contents and preventing the leakage of odors, etc. is still unsuccessful in preventing the leakage of odors, etc., and it is completely satisfactory. The reality is that it cannot be said. Furthermore, in the case of filling and packaging the above liquid seasoning and the like, as a base material film provided with a vapor deposition film of an inorganic oxide, those using a nylon film or the like are compared with those using a polyethylene terephthalate film, Due to the difference in the fragrance retaining property of the base film itself, there is a further problem that the fragrance retaining property is inferior. Thus, in the above case, for example, a transparent gas barrier obtained by laminating a gas barrier coating film of a sol-gel coating agent containing a metal alkoxide or a hydrolyzate thereof as a main material on a vapor-deposited film of an inorganic oxide. Although a hydrophilic film has also been proposed, the one using a nylon film or the like as the substrate film solves the problem that the aroma retaining property is inferior as compared with the one using a polyethylene terephthalate film or the like. The reality is that you cannot get it.

When a liquid or viscous content such as a liquid seasoning is filled and packaged as the content, the content of the laminate is affected by the content and the laminated material constituting the bag has high laminar strength. There is also a problem in that it is chipped and causes a peeling phenomenon or the like between the layers, so that it cannot be used.
Therefore, in order to improve the above-mentioned laminate strength and the like,
Pretreatment such as corona treatment may be carried out, but in the gas barrier film as described above, the effect is not recognized so much, and on the contrary, there is a problem that the vapor deposition film of the inorganic oxide is damaged. Further, in the above gas barrier film, generally, a vapor deposition film of an inorganic oxide is formed on one surface of a plastic substrate, and then the vapor deposition film surface of the inorganic oxide is subjected to gravure printing or the like. The desired print pattern layer is provided by the method, but at that time, the gas barrier film passes from the paper feeding to the winding side of the printing machine,
Pressure is applied to the gas barrier film between the various rolls constituting the printing machine, and cracks occur in the vapor deposition film of the inorganic oxide constituting the gas barrier film, thereby deteriorating the barrier property. There is a problem of doing. Further, the deterioration of the gas barrier property as described above is caused by providing the desired printed pattern layer on the gas barrier film, and then laminating another plastic film or the like, in the laminating step, the gas barrier film is formed. Since it passes from the paper feed of the coater to the take-up side, the pressure roll of the coater
There is also a problem that pressure or the like is applied to the gas barrier film between the gaps and the like to cause cracks or the like in the vapor deposition film of the inorganic oxide forming the gas barrier film, thereby deteriorating the barrier property. Therefore, in view of the above circumstances, the present invention has excellent transparency and high barrier properties against oxygen gas, water vapor, and the like, and transmits the aroma components contained in the contents to prevent odor leakage and the like. It has excellent fragrance retention,
Furthermore, it has excellent impact resistance, puncture resistance, storage stability for contents, etc., and is suitable for post-processing. It also has excellent laminate strength and is suitable for filling and packaging for liquid seasonings. It is an object of the present invention to provide a laminated material for packaging foods and a bag for packaging liquid seasonings using the same.

[0005]

Means for Solving the Problems As a result of various studies to solve the above problems, the present inventor has focused on a polyester resin having a rich aroma retaining property, and A one-layer or two-layer or more multilayer film of an inorganic oxide thin film is provided, and a perfuming primer containing a polyester resin as a main component of a vehicle is further provided on the above-mentioned inorganic oxide thin film.
A coating thin film is provided by the composition, and further, at least a heat-sealable resin layer is laminated on the coating thin film to form a laminated material. Use to make bags or boxes to make packaging bags, then
When a liquid or viscous content such as a liquid seasoning is filled and packaged in the packaging bag, it has excellent transparency and a high barrier property against oxygen gas or water vapor, and
Permeation of aroma components contained in the contents, excellent fragrance retention to prevent odor leakage, etc., further excellent impact resistance, puncture resistance, laminate strength, etc., also liquid such as liquid seasoning It has excellent storage stability for viscous contents, has no cracks during post-processing, and has extremely high suitability for post-processing. Furthermore, even if the packaged product is microwaved, it has sufficient suitability for microwave oven. However, the present invention has been completed by finding that it is possible to produce a laminated material having a suitability for filling and packing various liquid seasonings and the like as a packaging material and a packaging bag using the same.

That is, according to the present invention, one or two or more layers of inorganic oxide thin films are provided on one side of a substrate film, and a polyester-based polyester film is further provided on the inorganic oxide thin films. Perfuming primer with resin as the main component of vehicle
A coating thin film of the composition is provided, and further, at least a heat sealable resin layer is laminated on the coating thin film, and a laminated material for liquid seasoning packaging and the same. The present invention relates to a liquid seasoning packaging bag which is used for box making or bag making.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention described above will be described in more detail below. First, the constitution of a liquid seasoning packaging laminated material and a liquid seasoning packaging bag using the same according to the present invention will be described with reference to the drawings with reference to a few examples thereof. FIG. 1, FIG. 2 and FIG. FIG. 4 is a schematic cross-sectional view showing a layer structure of a laminated material for liquid seasoning packaging according to the present invention, and FIGS. 4 and 5 are bag-making using the laminated material for liquid seasoning packaging according to the present invention. It is a schematic perspective view which shows the structure of the liquid seasoning packaging bag which was boxed.

First, as shown in FIG. 1, a liquid seasoning packaging laminate A according to the present invention has one layer of an inorganic oxide thin film 2 or two layers on one surface of a substrate film 1. The above multi-layer film (not shown) is provided, and further, the thin film 2 of the inorganic oxide is provided with the thin coating film 3 of the aromatizing primer composition containing the polyester resin as the main component of the vehicle. Furthermore, the basic structure is that the coating thin film 3 has at least a heat-sealable resin layer 4 laminated thereon. As a specific example of the liquid seasoning packaging laminate according to the present invention, as shown in FIG. 2, in the liquid seasoning packaging laminate A shown in FIG. 1, the coating thin film is used. 3 and the heat-sealable resin layer 4, at least the heat-sealable resin layer 4 is laminated with the laminate adhesive layer 5 or the anchor coating agent layer 5a interposed therebetween. An example of the laminated material B for packaging a liquid seasoning is as follows. Furthermore, as another specific example of the laminated material for liquid seasoning packaging according to the present invention, as shown in FIG. 3, in the laminated material B for liquid seasoning packaging shown in FIG. A desired printed pattern layer 6 consisting of characters, figures, patterns, symbols, etc. is provided on the thin film 3, and then the adhesive layer 5 for laminating or the anchor layer is formed on the entire surface including the printed pattern layer 6. At least the heat-sealable resin layer 4 via the coating agent layer 5a.
The liquid-seasoning packaging laminated material C which is obtained by stacking Thus, the examples given above are a few examples of constituting the laminated material for liquid seasoning packaging according to the present invention,
The present invention is not limited to this. For example, although not shown in the present invention, in addition to the heat-sealable resin layer and the like, the purpose of use, the contents to be packed and packed, and the distribution channel. According to the sales form, the application, etc., other base materials can be arbitrarily laminated to design and manufacture various types of laminate materials for packaging liquid seasonings. In addition,
In the present invention, a thin film of an inorganic oxide, a coating thin film formed by a fragrance-preserving primer composition containing a polyester resin as a main component of a vehicle, an adhesive layer for laminate or an anchor coating layer It is important that the substrates are laminated in this order so as to be adjacent to each other in order to exert the effect of dense adhesion and the like.
It is possible to design and manufacture laminated materials for packaging liquid seasonings in various forms by arbitrarily stacking them depending on the use and the like.

Next, in the present invention, the constitution of the liquid seasoning packaging bag according to the present invention, which is formed by bag making or box making using the above-mentioned laminated material for liquid seasoning packaging, will be explained. As the liquid seasoning packaging bag, for example,
An example of the liquid seasoning packaging bag manufactured or formed by using the liquid seasoning packaging laminated material A shown in FIG. 1 will be described. As shown in the schematic perspective view of FIG. 2 of the liquid seasoning packaging laminates A and A are prepared, and the heat-sealing resin layers 4 and 4 located in the innermost layers are overlapped with the surfaces thereof facing each other, and then the edges around the outer periphery thereof. Hear the three sides of the club
The seal parts 7, 7 and 7 are formed by tossing to manufacture the three-way seal type liquid seasoning packaging bag D according to the present invention. Thus, in the above-mentioned three-way seal type liquid seasoning packaging bag D, the contents are filled from the upper opening, and then the opening is heat-sealed,
A variety of packaged products can be manufactured.

Alternatively, in the present invention, as the liquid seasoning packaging bag according to the present invention, as shown in the schematic perspective view of FIG. 5, the liquid seasoning packaging laminate A shown in FIG. 1 is used. The heat-sealable resin layers 4 and 4 located in the innermost layer are overlapped with the surfaces thereof facing each other, and then the two edges of the outer peripheral edge are heat-sealed. Part 7,
7 can be formed to produce the two-way seal type liquid seasoning packaging bag E according to the present invention. Thus, in the above-mentioned two-way seal type liquid seasoning packaging bag E, the contents are filled from the opening above the same as described above, and then the opening is heat-sealed. Various packaging products can be manufactured. It is needless to say that the present invention is not limited to the exemplary liquid seasoning packaging bag illustrated above, and its purpose,
It goes without saying that various types of bags for packaging liquid seasonings can be manufactured depending on the application and the like.

Next, in the present invention, the materials constituting the laminated material for packaging liquid seasoning, the bag for packaging liquid seasoning, etc. according to the present invention, the manufacturing method thereof, etc. will be explained. Various methods and the like can be adopted. First, in the present invention, as a base material film that constitutes a liquid seasoning packaging laminate material, a liquid seasoning packaging bag, etc. according to the present invention, when a liquid seasoning packaging bag is configured, it becomes a basic material. Therefore, it is possible to use a resin film or sheet having excellent properties in mechanical, physical, chemical, etc., in particular, having strength and toughness and heat resistance. Specifically, for example, toughness of polyester resin, polyamide resin, polyaramid resin, polyolefin resin, polycarbonate resin, polystyrene resin, polyacetal resin, fluorine resin, etc. Various resin films or sheets, and the like can be used. As the resin film or sheet, any of an unstretched film, a stretched film stretched in a uniaxial direction or a biaxial direction can be used, and the thickness of the film or sheet can be used. As a matter of fact,
5 μm to 100 μm, preferably 10 μm to 50 μm.

By the way, in the present invention, the above-mentioned base film is specifically excellent in impact resistance, puncture resistance and the like, and further has strength and toughness and heat resistance. It is preferable to use a polyamide resin film or sheet. Specifically, for example, nylon 46, nylon 6, nylon 66, nylon 610,
Various polyamide resins (nylon) such as nylon 612, nylon 7, nylon 11, nylon 12, etc.
Films or sheets can be used. The polyamide resin (nylon) film or sheet described above is stretched in the biaxial direction by a normal biaxial stretching method such as a tenter method or a tuber method. It is desirable to use a film or sheet of a 1 to 2 biaxially stretched polyamide resin (nylon) that has been stretched, and the film thickness thereof is preferably about 5 to 200 μm, and more preferably 10 to 100 μm. If necessary, the polyamide resin film or sheet may be subjected to surface smoothing treatment by coating an anchor coating agent or the like, and may be subjected to corona discharge treatment or plasma treatment. Surface treatment such as electric discharge treatment, ozone treatment, flame treatment, and the like can be arbitrarily performed. In the present invention, by using the film or sheet of the polyamide resin (nylon) as a base material as described above, the strength, impact resistance, puncture resistance and the like of the base material are utilized. It is possible to produce a laminated material for packaging liquid seasonings having those characteristics.

Next, in the present invention, a thin film of an inorganic oxide constituting the laminated material for packaging a liquid seasoning, a bag for packaging a liquid seasoning, etc. according to the present invention will be described. In particular, any thin film obtained by amorphizing a metal oxide can be used. For example, silicon (Si), aluminum (Al), magnesium (Mg), calcium (Ca), potassium (K). ), Tin (Sn), sodium (Na), boron (B), titanium (Ti), lead (Pb), zirconium (Zr), yttrium (Y) and other metal oxides are made amorphous. Thin films can be used. Thus, as a material suitable for a packaging material or the like, a thin film in which an oxide of a metal such as silicon (Si) or aluminum (Al) is made amorphous can be cited. Thus, a thin film obtained by making the above metal oxide amorphous is
It can be referred to as a metal oxide such as silicon oxide, aluminum oxide, magnesium oxide, etc., and its notation is MO _X such as SiO _X , AlO _X , MgO _X, etc.
(However, in the formula, M represents a metal element, and the value of X has a different range depending on the metal element.).
Further, as the range of the value of X, silicon (Si) is
0-2, aluminum (Al) 0-1.5, magnesium (Mg) 0-1, calcium (Ca) 0
~ 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 and 5, titanium (Ti) is 0 to 2,
Lead (Pb) is 0 to 1, zirconium (Zr) is 0 to
2, 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, as the packaging material, generally,
Examples other than silicon (Si) and aluminum (Al) are scarcely used, and silicon (Si) has a value within a range of 1.0 to 2.0, and aluminum (Al) has a value within a range of 0.5 to 1.5. Can be used.

In the present invention, as the inorganic oxide thin film, one layer of the above-mentioned inorganic oxide thin film,
Alternatively, an inorganic oxide thin film composed of two or more layers of inorganic oxide thin films is used. In the present invention, a method for forming a multi-layered film of one layer or two or more layers of a thin film of an inorganic oxide on a substrate film will be described. Examples of such a method include a vacuum vapor deposition method,
A physical vapor deposition method such as a sputtering method or an ion plating method (Physical Vapor Depos)
or chemical vapor deposition method such as plasma chemical vapor deposition method, thermochemical vapor deposition method, photochemical vapor deposition method (Chemical Vapor Dep method).
position method, CVD method) and the like. In the present invention, the above film forming method will be further described. For example, a vacuum vapor deposition method in which the metal oxide as described above is used as a raw material, which is heated and vaporized to be vapor-deposited on the base film, or , An oxidation reaction deposition method in which a metal or a metal oxide is used as a raw material, and oxygen is introduced to oxidize and deposit on a base film, and further, a plasma-assisted oxidation reaction deposition in which the oxidation reaction is supported by plasma The vapor deposition film can be formed by using a method or the like. Further, in the present invention, when forming a vapor deposited film of silicon oxide, the vapor deposited film can be formed by a plasma chemical vapor deposition method using organosiloxane or the like as a raw material. In the present invention, the thickness of the above-mentioned inorganic oxide thin film varies depending on the type of metal or metal oxide used, but for example, the thickness of one layer of the inorganic oxide thin film is 50- 2000
Å position, preferably 100-1000 Å position is desirably selected and formed, and the thickness of the multilayer film of two or more layers of the inorganic oxide thin film is 100-1000.
It is desirable to have a position of 4000Å, preferably 120 to 2000Å.

In the present invention, a specific example of the method for forming a multi-layer film of one layer or two or more layers of an inorganic oxide thin film will be given. FIG. 6 shows an example of a winding type vacuum vapor deposition machine. It is a schematic block diagram. As shown in FIG. 6, in the vacuum chamber 111, the substrate film 113 fed from the unwinding roll 112 is a coating drum 114.
And into the vapor deposition chamber-115, where the vapor deposition source heated by the crucible 116 is vaporized, and if necessary, oxygen or the like is jetted from the oxygen outlet 117 while cooling the above-mentioned vaporized chamber. -The vapor deposition film of the inorganic oxide is formed on the base film 113 on the coating drum 114 through the masks 118, 118, and then the base film 113 on which the vapor deposition film is formed is sent into the vacuum chamber-111. Then, by winding the film on a winding roll 119, a base film 11 having a thin film of an inorganic oxide.
3 can be manufactured. Thus, in the present invention, the film formation as described above is repeated, or, although not shown, two or more roll-up type vacuum vapor deposition machines such as those described above are connected to form a continuous vapor deposition. By doing
It is possible to form a thin film of an inorganic oxide comprising a multilayer film of two or more thin films of an inorganic oxide.

In the present invention, a specific example of the method of forming a multilayer film of one or more inorganic oxide thin films by the above-described plasma enhanced chemical vapor deposition will be illustrated. It is a schematic block diagram which illustrates an example of a chemical vapor deposition apparatus. As shown in FIG. 7, the substrate film 214 is unwound from the unwinding roll 213 arranged in the vacuum chamber-212 of the plasma enhanced chemical vapor deposition apparatus 211, and further, at a constant speed via the auxiliary roll 215. A raw material supply nozzle is provided with a mixed gas that is conveyed and then supplied from the raw material volatilization supply devices 217, 218, and 219 on the peripheral surface of the cooling / electrode drum 216, for example, an organic silicon compound, oxygen gas, inert gas, or the like. Introduced through 220, the glow discharge plasma 221 forms a thin film of an inorganic oxide such as a vapor deposition film of silicon oxide on one surface of the base film 214 to form a film, and the cooling / electrode drum 216 Is applied with a predetermined voltage from a power source 222 arranged outside the vacuum chamber-212, and a magnet is provided near the cooling / electrode drum 216. The base film 214 on which a thin film of inorganic oxide such as a vapor deposition film of silicon oxide is formed is wound up by the auxiliary roll 215. The base film 214 having a thin film of the inorganic oxide can be manufactured by winding the base film 214 on the reel 224. Thus, in the present invention, the film formation as described above is repeated or, although not shown, two or more plasma chemical vapor deposition devices as described above are continuously connected to perform vapor deposition. This makes it possible to form a thin film of an inorganic oxide, which is composed of a multilayer film of two or more layers of a thin film of an inorganic oxide. In the figure, 225 represents a vacuum pump.

Further, in the present invention, as a method for forming a multilayer film of two or more layers of inorganic oxide thin films, physical vapor deposition such as the above-mentioned vacuum deposition method, sputtering method, ion plating method, etc. Method (Physical Vap
or Deposition method, PVD method), plasma chemical vapor deposition method, thermochemical vapor deposition method, photochemical vapor deposition method, and other chemical vapor deposition methods (Chemical Vapor Deposition method).
Deposition method, CVD method), and by forming two or more layers of inorganic oxide thin films composed of both of them to form a film, an inorganic film composed of two or more layers of inorganic oxide thin films. It is also possible to produce thin oxide films. That is, although not shown, first, a thin film of the first inorganic oxide is formed by using the above-described winding type vacuum deposition machine, and then the above-mentioned plasma chemical vapor deposition is formed on the thin film of the inorganic oxide. A second inorganic oxide thin film is formed by using the apparatus, and the first and second inorganic oxide thin films form an inorganic oxide thin film including two or more layers of inorganic oxide thin films. Can be formed. In the above,
The film formation may be performed in any order, for example, a roll-up vacuum vapor deposition machine may be used first to form a film, and then a plasma chemical vapor deposition apparatus may be used to form a film, and vice versa. The film may be formed by.

In the above, the thin film mainly composed of the vapor-deposited film of silicon oxide as the thin film of the inorganic oxide comprises a silicon compound containing at least silicon and oxygen as constituent elements,
Further, it is preferable that one or more elements of carbon or hydrogen are contained as a trace constituent element, and the film thickness thereof is within a range of 50 to 500 Å. Thus, in the present invention, as the above-mentioned silicon oxide thin film, a vapor deposition film formed by using a plasma chemical vapor deposition method using an organic silicon compound as a raw material and utilizing a low temperature plasma generator or the like is used. be able to. In the above, examples of the organosilicon compound include 1.1.3.3-tetramethyldisiloxane, hexamethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethyl. Silane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane,
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 because of its handleability and vapor deposition film formed. It is a particularly preferable raw material in view of the characteristics and the like. Further, 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 can be used.
In the present invention, in order to obtain highly active and stable plasma, it is desirable to use a high frequency plasma generator.

Next, in the present invention, a fragrance-preserving primer composition containing a polyester resin as a main component of a vehicle, which constitutes a laminated material for packaging a liquid seasoning, a bag for packaging a liquid seasoning according to the present invention, is used. Explaining the coating thin film, examples of the polyester resin constituting the above-mentioned fragrance-preserving primer composition include one or more aromatic saturated dicarboxylic acids having a benzene nucleus such as terephthalic acid as a basic skeleton. , A thermoplastic polyester resin produced by polycondensation with one or more saturated divalent alcohols can be used. In the above, as the aromatic saturated dicarboxylic acid having a benzene nucleus as a basic skeleton, for example, terephthalic acid, isophthalic acid, phthalic acid, diphenylether-4,4-dicarboxylic acid, and the like 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, Aliphatic glycols such as polytetramethylene glycol, hexamethylene glycol, dodecamethylene glycol and 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, specific examples of the polyester resin include thermoplastic polyethylene terephthalate resin produced by polycondensation of terephthalic acid and ethylene glycol, terephthalic acid and tetramethylene glycol. Thermoplastic polybutylene terephthalate resin produced by polycondensation with styrene, thermoplastic polycyclohexane dimethylene terephthalate resin produced by polycondensation of terephthalic acid and 1,4-cyclohexane dimethanol, terephthalate Thermoplastic polyethylene terephthalate resin produced by copolycondensation of acid, isophthalic acid and ethylene glycol, produced by copolycondensation of terephthalic acid, ethylene glycol and 1,4-cyclohexane dimethanol Thermoplastic polyethylene terephthalate resin,
Thermoplastic polyethylene terephthalate resin, polyester polyol resin, etc. produced by copolycondensation of terephthalic acid, isophthalic acid, ethylene glycol and propylene glycol 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 , One or more of aliphatic saturated dicarboxylic acids such as dodecanoic acid may be added to carry out copolycondensation, and the amount thereof is 1 to 1 with respect to the aromatic saturated dicarboxylic acid having a benzene nucleus as a basic skeleton. About 10% by weight is preferably added and used. Further, in the present invention, among the polyester resins as described above, one or more aromatic saturated dicarboxylic acids having a benzene nucleus as a basic skeleton such as terephthalic acid and one or more saturated divalent alcohols. In producing a thermoplastic polyester resin by polycondensation with the above, one or more saturated divalent alcohols are excessively added to the aromatic saturated dicarboxylic acid having a benzene nucleus such as terephthalic acid as a basic skeleton. It is preferable to use a thermoplastic polyester polyol resin produced by polycondensing one or more acids with one or more saturated divalent alcohols.

Thus, in the present invention, the aroma-retaining primer containing the above polyester resin as the main component of the vehicle.
The composition comprises one or more of the above polyester resins as the main component of the vehicle, and if necessary, for example, a silane coupling agent, a filler, a stabilizer,
One or more additives such as a curing agent, a cross-linking agent, a lubricant, an ultraviolet absorber and the like are optionally added, and a solvent, a diluent and the like are added and sufficiently kneaded to obtain a fragrance-preserving primer composition. adjust. Then, in the present invention, the above-mentioned fragrant primer composition is applied to, for example, roll coat, gravure coat, knife coat, dep coat, spray coat.
Coating or other coating method on the thin film of the inorganic oxide, and then the coating film is dried to remove the solvent, the diluent and the like. -A coating thin film according to the present invention can be formed by subjecting it to a aging treatment or the like. In the present invention,
The film thickness of the coating thin film formed by the aromatizing primer composition is, for example, about 0.01 to 50 μm, preferably 0.1 to 5 μm. In addition, in the above fragrance-preserving primer composition, for example, a curing agent such as a polyfunctional isocyanate compound is added, and a polyester resin is crosslinked or cured to form a coating thin film, thereby forming an inorganic substance. It is possible to improve the close adhesion between the oxide thin film and the heat-sealable resin layer, and prevent permeation-preventing components from permeating the contents, preventing the odor from leaking and the like. It has the advantage of being able to improve.

Next, in the present invention, a heat-sealable resin forming a heat-sealable resin layer constituting a laminated material for liquid seasoning packaging, a bag for liquid seasoning packaging, etc. according to the present invention. As the material, a resin film or sheet that can be melted by heat and fused to each other can be used. Specifically, for example, low density polyethylene, medium density polyethylene, high density polyethylene, linear ( (Linear) low density polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-acrylic acid copolymer, ethylene-ethyl acrylate copolymer, ethylene-
Methacrylic acid copolymer, ethylene-methyl methacrylate copolymer, ethylene-propylene copolymer, methylpentene polymer, polybutene polymer, polyolefin resin such as polyethylene or polypropylene acrylic acid, methacrylic acid, maleic acid, anhydrous Films of resins such as acid-modified polyolefin resins modified with unsaturated carboxylic acids such as maleic acid, fumaric acid, itaconic acid, polyvinyl acetate resins, poly (meth) acrylic resins, polyvinyl chloride resins, etc. Or a sheet can be used. Thus, the above film or sheet can be used in the state of a coating film made of a composition containing the resin. The thickness of the film, film or sheet is preferably about 5 μm to 300 μm, more preferably about 10 μm to 150 μm.

In the present invention, the above-mentioned heat seal
The heat-sealable resin forming the resinous resin layer is not particularly limited, but it is particularly preferable to use an ethylene / α-olefin copolymer polymerized using a metallocene catalyst. is there. Thus, as the ethylene / α-olefin copolymer polymerized using the above metallocene catalyst, for example, a catalyst formed by combining a metallocene complex and an alumoxane such as a catalyst formed by combining zirconocene dichloride and methylalumoxane, that is, Ethylene produced by polymerization using a metallocene catalyst
An α-olefin copolymer can be used. The metallocene catalyst is also called a single-site catalyst because the active site is not uniform and is called a multi-site catalyst, whereas the metallocene catalyst is called a single-site catalyst because the active sites are uniform. Specifically, the product name “Car” manufactured by Mitsubishi Chemical Corporation
"Nell", product name "Evolu" manufactured by Mitsui Petrochemical Industry Co., Ltd., USA, EXXON CH
Product name "EXACACT" (EXAC) manufactured by EMICAL
T) ", Dow Chemical, USA
AL) product name "Affinity- (AFFINIT
Y), an ethylene / α-olefin copolymer polymerized with a metallocene catalyst such as "ENGAGE" under the trade name can be used.

In the present invention, the resin of the ethylene / α-olefin copolymer polymerized by using the metallocene catalyst as described above is a film or a sheath thereof.
Or an extrusion copolymer made of a composition containing a copolymer thereof.
It can be used in the form of a coating film or the like, whereby it functions as a film or sheet of a resin having a heat seal forming the innermost layer, and thus the low temperature heat seal thereof. Due to the property, it is possible to prevent the occurrence of cracks or the like that occur in the inorganic oxide thin film or the like during post-processing such as bag making. The thickness of the film or film or sheet is 3 μm to 300 μm.
Position, preferably 5 μm to 100 μm. In addition, in the present invention, the ethylene-α-olefin copolymer obtained by polymerization using the metallocene catalyst is further added to, for example, partially crosslinked ethylene-propylene rubber (EPDM) and ethylene-propylene rubber (EP
R), styrene-butadiene-styrene block copolymer (SBS), styrene-isobutylene-styrene block copolymer (SIS), styrene-ethylene-
It is also possible to use a heat-sealable resin layer made of a resin composition containing one or more thermoplastic elastomers such as butylene-styrene block copolymer (SEBS). Further, in the present invention, the ethylene-α-olefin copolymer obtained by polymerization using the above metallocene catalyst is further added to, for example, a heat-sheath resin forming the above-mentioned heat-sealable resin layer. It is also possible to use a heat-sealable resin layer made of a resin composition obtained by adding one or more types of resin. Further, in the present invention, as the heat-sealable resin layer, for example, linear low density polyethylene and an ethylene-α-olefin copolymer obtained by polymerization using a metallocene catalyst are used. It may be a heat-sealable resin layer having a multi-layered structure obtained by coextruding the above.

Next, in the present invention, as a method for laminating the heat-sealable resin layer on the coating thin film surface, for example, laminating adhesive with a laminating adhesive is used. A dry lamination method of laminating via an agent layer, or an extrusion lamination method of laminating via a melt-extruded resin layer made of a melt-extruded adhesive resin can be used. In the above, examples of the adhesive for laminate include, for example, one-component or two-component type cured or non-cured vinyl type, (meth) acrylic type,
Solvent type such as polyamide type, polyester type, polyether type, polyurethane type, epoxy type, rubber type, etc.,
An aqueous type or emulsion type adhesive for laminate can be used. Thus, the above-mentioned Lamine
Examples of the coating method of the adhesive for the substrate include direct gravure roll coat method, gravure roll coat method, kiss coat method, river roll coat method, fonten method, transfer roll. It can be applied by a method such as a rukot method or the like, and as the coating amount,
0.1 to 10 g / m ² (dry state), more preferably 1 to 6 g / m ² (dry state) is desirable. In addition,
In the present invention, an adhesion promoter such as a silane coupling agent can be optionally added to the above-mentioned adhesive for laminate.

Next, in the above, as the melt-extruded adhesive resin, the above-mentioned thermoplastic resin forming the heat-sealable resin layer can be similarly used. Thus, in the present invention, it is preferable to use low-density polyethylene, particularly linear low-density polyethylene, or acid-modified polyethylene as the melt-extruded adhesive resin. The thickness of the melt-extruded resin layer formed by the melt-extruded adhesive resin is about 5 to 100 μm,
More preferably, about 10 to 50 μm is desirable. In addition,
In the present invention, when it is necessary to obtain a stronger adhesive strength when laminating by the above extrusion lamination method, for example, an anchor is formed on the coating thin film surface.
It is also possible to coat an adhesion improver such as a coating agent.
Specific examples of the anchor coating agent include organic titanium-based anchor coatings such as alkyl titanate.
Various anchor coating agents such as water-based or oil-based anchor coating agents, isocyanate-based anchor coating agents, polyethyleneimine-based anchor coating agents, polybutadiene-based anchor coating agents, etc. Can be used. Thus, in the present invention, the above anchor coating agent is used, for example, in roll coating, gravure coating, knife coating, dip coating, spray coating, and other coating methods. And
Coating, dry the solvent, diluent, etc.
A coating agent layer can be formed. In the above, the coating amount of the anchor coating agent is preferably about 0.1 to 5 g / m ² (dry state).

In the present invention, as the above-mentioned laminate adhesive, in particular, a film is formed by a curing reaction between polyester polyol or polyether polyol and isocyanate, and the adhesive for laminate is formed. It is preferable to form using an agent. Specifically, polymers obtained by reacting a polyfunctional isocyanate with a hydroxyl group-containing compound, such as tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate, etc. Aromatic polyisocyanates, or polyfunctional isocyanates such as aliphatic polyisocyanates such as hexamethylene diisocyanate and xylylene diisocyanate, and polyether polyols, polyester polyols, and polyacrylates. -A one-part or two-part type curable polyurethane resin obtained by reaction with a hydroxyl group-containing compound such as topolol is used as a vehicle main component, and an adhesive composition for laminate is used. , Roll coat, gravure coat, knife coat, dep coat, spray coat
Coating with other coating methods, solvent,
The diluent or the like can be dried to form the laminate adhesive layer constituting the laminated material according to the present invention. In the above, the film thickness of the adhesive layer for lamination is 0.
It is preferably about 1 to 6 g / m ² (dry state). Thus, in the present invention, by using the polyurethane-based resin as described above, the degree of elongation of the thin film constituting the adhesive layer for laminate is improved, and, for example, laminating or bag making. The purpose of this is to improve suitability for post-processing such as processing and prevent the occurrence of cracks and the like in the thin film of the inorganic oxide during the post-processing.

By the way, in the present invention, a laminer formed into a film by a curing reaction between polyester polyol or polyether polyol and isocyanate which constitute the above-mentioned laminated material for packaging liquid seasonings according to the present invention. As the adhesive layer for the belt, 300 mm / m under the environment of 23 ° C. and 50% RH with No. 4 dumbbell according to JIS K6301.
in. It is desirable that the film has a tensile elongation of 300% to 550% when measured under the speed condition of. In the present invention, the tensile elongation of the adhesive layer for laminate synergizes with the above-mentioned coating thin film or the like to form a thin film of an inorganic oxide or a coating thin film which constitutes a laminated material for liquid seasoning packaging. , The adhesive property for laminate, the heat-sealing resin layer, and the like are improved in tight adhesion, thereby preventing the occurrence of cracks and the like in the thin film of the inorganic oxide. In the above, if the tensile elongation is less than 300%, it lacks flexibility and is not preferable because cracks or the like occur in the thin film of the inorganic oxide in the post-processing such as laminate or bag making or box making. Also, the tensile elongation is 55
If it exceeds 0%, the flexibility becomes excessive and the tearability is poor, and for example, the unsealing property of the packaging container is poor, which is not preferable.

In the liquid seasoning packaging laminated material according to the present invention, a printed pattern layer composed of, for example, characters, figures, patterns, symbols, etc. is formed on any of the layers constituting the layered product. You can As the above-mentioned printed pattern layer, specifically, for example, a usual gravure ink composition on a coating thin film of the above-mentioned polyester resin as the main component of the vehicle is a fragrance-imparting primer composition. Using an ink composition such as an offset ink composition, a letterpress ink composition, a screen ink composition, etc., for example, a gravure printing method, an offset printing method,
Printing methods such as letterpress printing method, silk screen printing method, etc. are used, for example, characters, figures, patterns, symbols,
It can be configured by forming a desired print pattern composed of others. In the above, since a desired printed pattern layer is formed on the coating thin film, compared with the case where the desired printed pattern layer is formed on the thin film of the inorganic oxidized part, the thin film of the inorganic oxidized part is formed. This has the advantage that the occurrence of cracks and the like can be reduced.

Next, in the present invention, as a material constituting the laminated material for packaging liquid seasonings, the bag for packaging liquid seasonings, etc. according to the present invention, for example, low density polyethylene having a barrier property against water vapor, water and the like. Films or sheets of resin such as medium density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene and ethylene-propylene copolymer, or polyvinyl alcohol having barrier properties against oxygen, water vapor, etc. , A film or sheet of a resin such as a saponified product of ethylene-vinyl acetate copolymer, a colorant such as a pigment to the resin, and other desired additives and kneaded to form a film having various light-shielding properties The colored resin film or sheet of the above 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 further 10 μm to 100 μm.
Rank is desirable.

In the present invention, the packaging container is usually subjected to severe physical and chemical conditions. Therefore, the packaging material constituting the packaging container is required to have strict packaging suitability. Therefore, various conditions such as deformation prevention strength, drop impact strength, pinhole resistance, heat resistance, sealing performance, quality maintenance, workability, hygiene, etc. are required. , A material satisfying the above conditions can be arbitrarily selected and used, and specifically, for example, low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, Ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ionomer-resin, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid or methacrylic acid copolymer, Cylpentene polymer, polybutene resin, polyvinyl chloride resin, polyvinyl acetate resin, polyvinylidene chloride resin, vinyl chloride-vinylidene chloride copolymer, poly (meth) acrylic resin, polyacrylonitrile resin, Polystyrene resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), polyester resin, polyamide resin, polycarbonate resin, polyvinyl alcohol -Based resin, saponified ethylene-vinyl acetate copolymer, fluorine-based resin,
Any known film or sheet of a known resin such as a diene resin, a polyacetal resin, a polyurethane resin, nitrocellulose, etc. can be selected and used. In addition, for example, a film such as cellophane, synthetic paper, or the like can 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 is from several μm to 3 μm.
It can be used by selecting from the range of about 00 μm.
Further, in the present invention, the film or sheet may be any film such as an extrusion film, an inflation film, and a coating film. In addition, in the present invention, any one of layers constituting the laminated material according to the present invention is desired to be formed of characters, figures, patterns, symbols, etc. by offset printing, gravure printing, silk screen printing, etc. It goes without saying that a printed pattern layer can be formed.

Next, in the present invention, a method of making a bag or box using the above-mentioned laminated material for packaging liquid seasoning will be explained. For example, in the case of a soft packaging bag made of a plastic film or the like, Using the liquid seasoning packaging laminate produced by the method as described above, the inner surface of the heat sealable resin layer is made to face, and it is folded or folded.
Alternatively, stack the two pieces together and then heat the peripheral edge.
The bag body can be constructed by providing a seal portion by tossing. Thus, as the bag-making method, the above liquid seasoning packaging laminated material is bent with the surfaces of its inner layers facing each other, or two of them are overlapped, and further the peripheral end portion of the outer periphery thereof, For example, side seal type, two-way seal type, three-way seal type, four-way seal type, envelope sticking seal type, gassho sticking seal type (pillow seal type), pleats For heat-sealing with attached seal type, flat-bottomed seal type, square-bottomed seal type, and other heat-sealed types, for packaging various liquid seasonings according to the present invention Bags can be manufactured. Other,
For example, it is possible to manufacture a self-supporting packaging bag (standing pouch), and further, in the present invention, a tube container and the like can be manufactured using the above-mentioned laminated material for liquid seasoning packaging. it can. In the above, as a heat seal method, for example, a bar seal or a rotary roll seal is used.
Belt, belt seal, impulse seal, high frequency seal,
It can be performed by a known method such as ultrasonic sealing. In the present invention, the liquid seasoning packaging bag as described above may be optionally attached with a spout such as a one-piece type, a two-piece type, or the like, or a zipper for opening and closing. it can.

In the present invention, the liquid seasoning packaging bag produced as described above is used for filling and packaging liquid or viscous articles such as various liquid seasonings, or processed products thereof. is there. Thus, in the present invention,
In the liquid seasoning packaging bag according to the present invention, a liquid or viscous content such as a liquid seasoning, or when filling and packaging the processed product or the like, the content contains a component rich in permeability, which is Since it affects the inner surface of the bag and often causes phenomena such as delamination, it may not be useful.
In the laminated material constituting the bag, the peel strength in water between the thin film of the inorganic oxide constituting the laminated material and the heat-sealable resin layer is 50 g / 15 mm width or more, and
The peel strength at 25 ° C. is preferably 200 g / 15 mm width or more. In the above, if the peel strength in water is less than 50 g / 15 mm width, for example, in the case of applications such as sterilization in hot water such as boil and retort, or when used under high humidity, packaging material As a result, sufficient strength cannot be obtained and, for example, oxygen gas barrier properties and the like are deteriorated.
A peel strength of less than 200 g / 15 mm width at 5 ° C. is not preferable because practical strength as a packaging material cannot be obtained. The laminated material for packaging a liquid seasoning according to the present invention can be used as a lid material, for example, by being attached to a flange portion of a plastic molding container.

[0034]

EXAMPLES The present invention will be described more specifically with reference to examples. Example 1 First, on a surface of a biaxially stretched nylon 6 film having a thickness of 15 μm, using a chemical vapor deposition method (CVD), a thickness of 2 was obtained.
A vapor deposited film of 00Å silicon oxide was formed. Next, a thermoplastic polyester polyol resin as the main component of the vehicle,
A perfuming primer composition containing a small amount of a polyfunctional isocyanate compound was prepared (solid content 8%). next,
Using the above fragrance-preserving primer composition, a 200 Å-thick silicon oxide vapor-deposited film surface formed as described above was coated using a gravure roll coat method, and then 10
It was dried at 0 ° C. for 5 seconds to form a coating thin film (thickness 0.3 g / m ² , dry state) by the above-mentioned fragrance retaining primer composition. Then, a 7% ethyl acetate / toluene solution of a two-component curing type polyurethane resin consisting of polyester polyol and isocyanate was formed on the surface of the coating thin film formed by the fragrance-preserving primer composition. The laminator adhesive is used to form a laminate adhesive layer by coating it with a gravure roll coating method to a film thickness of 3 μm, and then the laminate adhesive layer is formed. The linear low-density polyethylene and ethylene-α-olefin polymerized by using a metallocene catalyst are used on the adhesive layer surface for co-extrusion, and these are co-extruded to a thickness of 30 μm and a co-extrusion of a thickness of 60 μm. A heat-sealable resin layer made of a film was formed to produce a laminated material for liquid seasoning packaging according to the present invention having the following layer constitution. Biaxially Stretched Nylon 6 Film, Silicon Oxide Deposition Film / Co-
Thin film / laminate adhesive layer / heat-sealable resin layer Next, using the liquid seasoning packaging laminate prepared above, a three-way seal type plastic is produced by a di-roll filling and packaging machine. When a bag-making product is manufactured and a liquid seasoning is filled, and then the opening is heat-sealed to manufacture a packaged product, it has a high barrier property and deterioration of the barrier property is also recognized. In addition, it is also excellent in fragrance retention, and moreover, it is a laminer
Very good results with excellent strength were obtained.

Example 2 First, a vapor-deposited film of aluminum oxide having a thickness of 200 Å was formed on one surface of a biaxially stretched nylon 6 film having a thickness of 15 μm by physical vapor deposition (PVD). Next, a thermoplastic polyester polyol resin was used as a main component of the vehicle, and a fragrance-imparting primer composition containing a small amount of a polyfunctional isocyanate compound was prepared (solid content 8).
%). Next, the above-mentioned fragrance-preserving primer composition was used to coat the 200 Å-thick aluminum oxide vapor-deposited film surface formed above using a gravure roll coating method, and then, It was dried at 100 ° C. for 5 seconds to form a coating thin film (thickness: 0.3 g / m ² , dry state) using the above-mentioned fragrance retaining primer composition. On the surface of the coating thin film formed as described above, a laminer composed of a 7% ethyl acetate and toluene solution of a two-component curing type polyurethane resin composed of polyetherpolyol and isocyanate.
A gluing roll coating method is used to coat the gluing roll adhesive to a film thickness of 3 μm to form a laminating adhesive layer, and then the laminating adhesive is used. On the agent layer surface, using linear low density polyethylene and ethylene-α-olefin polymerized using a metallocene catalyst,
Each of these is co-extruded to a thickness of 30 μm to obtain a thickness of 60
A heat-sealable resin layer made of a co-extruded film having a thickness of μm was formed to produce a liquid seasoning packaging laminate according to the present invention having the following layer structure. Biaxially stretched nylon 6 film / aluminum oxide deposited film / coating thin film / laminate adhesive layer / heat-sealable resin layer Next, using the liquid seasoning packaging laminate prepared above , A three-way seal type plastic bag was manufactured by a di-roll filling and packaging machine, liquid seasoning was filled, and then the opening was heat-sealed to produce a packaged product. It has excellent barrier properties, no deterioration of the barrier properties is observed, and it is also excellent in fragrance retention.
Very good results with excellent strength were obtained.

Example 3 First, on one surface of a biaxially stretched nylon 6 film having a thickness of 15 μm, a vapor deposition film of silicon oxide having a thickness of 150 Å was formed into a two-layer structure by chemical vapor deposition (CVD). Then, a multilayer film was formed. Next, using the fragrance-preserving primer composition produced in Example 1 above, in the same manner as in Example 1 above, a co-deposited film of silicon oxide constituting the multilayer film formed above was coated with A coating thin film (thickness 0.3 g / m ² , dry state) was formed. Next, on the surface of the coating thin film formed as described above, a two-part curable polyurethane-based resin consisting of polyether polyol and isocyanate was adhered for lamination using 7% ethyl acetate and toluene solution. An agent is used, and this is coated by a gravure roll coat method to a film thickness of 3 μm to form an adhesive layer for laminate, and then, on the adhesive layer surface for laminate, A sheet made of linear low density polyethylene and ethylene-α-olefin polymerized using a metallocene catalyst, each of which is coextruded to a thickness of 30 μm, and which is a coextrusion film having a thickness of 60 μm. The resinous resin layer was formed to produce a liquid seasoning packaging laminate according to the present invention having the following layer structure. Biaxially stretched nylon 6 film / silicon oxide vapor deposition film 2 layers /
Coating thin film / laminate adhesive layer / heat sheet
Resinous layer, then using the liquid seasoning packaging laminate produced above, to produce a three-way seal type plastic bag with a di-roll filling and packaging machine and fill the liquid seasoning with When a packaged product is manufactured by heat-sealing the opening, it has a high degree of barrier property, no deterioration of the barrier property is observed, and the fragrance is excellent, and further, the laminin
Very good results with excellent strength were obtained.

Example 4 First, on one side of a biaxially stretched nylon 6 film having a thickness of 15 μm, a thickness of 2 was obtained by physical vapor deposition (PVD).
Two layers of vapor-deposited aluminum oxide film of 00Å were laminated to form a multilayer film. Next, using the fragrance preserving primer composition produced in Example 2 above, in the same manner as in Example 2 above, the aluminum oxide deposited film surface constituting the multilayer film formed above was coated with -Ting thin film (thickness 0.3g /
m ² , dry state). Next, on the surface of the coating thin film formed as described above, an adhesive for laminating composed of a 7% ethyl acetate and toluene solution of a two-component curing type polyurethane resin composed of polyester polyol and isocyanate Was coated with a gravure roll coat method to a film thickness of 3 μm to form an adhesive layer for laminate, and then on the adhesive layer surface for laminate,
A sheet made of linear low density polyethylene and ethylene-α-olefin polymerized using a metallocene catalyst, each of which is coextruded to a thickness of 30 μm, and which is a coextrusion film having a thickness of 60 μm. The resinous resin layer was formed to produce a liquid seasoning packaging laminate according to the present invention having the following layer structure. Biaxially stretched nylon 6 film / aluminum oxide vapor deposition film 2 layers / coating thin film / laminate adhesive layer / heat sealable resin layer Next, the above-prepared liquid seasoning packaging laminate material is used. Used to produce a three-way seal type plastic bag with a di-roll filling and packaging machine and to fill it with liquid seasoning, and then heat seal the opening to produce a packaged product. It has a high barrier property, no deterioration of the barrier property is observed, and it is also excellent in fragrance retention.
Very good results with excellent strength were obtained.

Example 5 On one side of a biaxially stretched nylon 6 film having a thickness of 15 μm, a thickness of 200Å was formed by chemical vapor deposition (CVD).
A silicon oxide vapor-deposited film is formed on the silicon oxide vapor-deposited film, and a thickness of 2 is formed on the silicon oxide vapor-deposited film by physical vapor deposition (PVD).
A vapor deposition film of 00Å aluminum oxide was formed, and two vapor deposition films were overlaid to form a multilayer film. Next, using the fragrance preserving primer composition produced in Example 2 above, in the same manner as in Example 2 above, the aluminum oxide deposited film surface constituting the multilayer film formed above was coated with A coating thin film (thickness 0.3 g / m ² , dry state) was formed. next,
On the coating thin film surface formed as described above, a laminate adhesive composed of a 7% ethyl acetate and toluene solution of a two-component curing type polyurethane resin composed of polyester polyol and isocyanate was used. This is coated with a gravure roll coat method to a film thickness of 3 μm to form a laminate adhesive layer, and then a linear low density is formed on the laminate adhesive layer surface. A heat seal comprising polyethylene and an ethylene-α-olefin copolymer polymerized using a metallocene catalyst, each of which is coextruded to a thickness of 30 μm, and which is a coextruded film having a thickness of 60 μm. The resinous resin layer was formed to produce a laminated material for liquid seasoning packaging according to the present invention having the following layer structure. Biaxially stretched nylon 6 film, silicon oxide vapor deposition film, aluminum oxide vapor deposition film / coating thin film / laminate
Adhesive layer for heat / heat sealable resin layer Next, using the laminate for packaging liquid seasoning prepared above, a three-way seal type plastic bag is manufactured by a die roll filling and packaging machine. A liquid seasoning was filled together with the liquid seasoning, and then the opening was heat-sealed to produce a packaged product, which had a high barrier property and no deterioration in the barrier property was observed. It has excellent fragrance and is also a laminée.
Very good results with excellent strength were obtained.

Example 6 First, on one side of a biaxially stretched nylon 6 film having a thickness of 15 μm, a thickness of 2 was obtained by physical vapor deposition (PVD).
A vapor deposition film of 00Å aluminum oxide is formed, and then, a chemical vapor deposition method (C
VD) was used to form a vapor deposition film of silicon oxide having a thickness of 200Å, and two vapor deposition films were overlaid to form a multilayer film. Next, using the fragrance-preserving primer composition produced in Example 1 above, in the same manner as in Example 1 above, a co-deposited film of silicon oxide constituting the multilayer film formed above was coated with A coating thin film (thickness 0.3 g / m ² , dry state) was formed.
On the coating thin film surface formed as described above, a laminate adhesive composed of a 7% ethyl acetate and toluene solution of a two-component curing type polyurethane resin composed of polyetherpolyol and isocyanate is used. Then, using a gravure roll coating method, this was coated to a film thickness of 3 μm to form an adhesive layer for lamination, and then the laminate was formed.
The linear low density polyethylene and the ethylene-α-olefin copolymer polymerized by using a metallocene catalyst are used for the adhesive layer surface for the sheet, and these are coextruded to a thickness of 30 μm, and a thickness of 60 μm. A heat-sealing resin layer made of the coextruded film of 1. was formed to produce a liquid seasoning packaging laminate according to the present invention having the following layer structure. Biaxially stretched nylon 6 film / aluminum oxide vapor deposition film / silicon oxide vapor deposition film / coating thin film / laminate
Adhesive layer for heat / heat sealable resin layer Next, using the laminate for packaging liquid seasoning prepared above, a three-way seal type plastic bag is manufactured by a die roll filling and packaging machine. A liquid seasoning was filled together with the liquid seasoning, and then the opening was heat-sealed to produce a packaged product, which had a high barrier property and no deterioration in the barrier property was observed. It has excellent fragrance and is also a laminée.
Very good results with excellent strength were obtained.

Example 7 In Example 1 above, a laminate adhesive layer was formed on the coating thin film surface of the fragrance-preserving primer composition, and then the laminate adhesive layer was formed. Instead of forming a heat-sealable resin layer composed of a co-extruded film having a thickness of 60 μm composed of linear low-density polyethylene and ethylene-α-olefin polymerized by using a metallocene catalyst on the layer surface, a fragrance Using a linear low-density polyethylene on the surface of the coating thin film with a conductive primer composition,
While linearly melt extruding it to a thickness of 20 μm via an anchor coating agent, linear low density polyethylene and ethylene-α-olefin polymerized using a metallocene catalyst were used in advance, and A 60 μm-thick coextrusion film formed by coextrusion to a thickness of 30 μm was extrusion-laminated, and otherwise the same as in Example 1 above, to obtain the present invention having the following layer structure. Such a liquid seasoning packaging laminate was produced. Biaxially Stretched Nylon 6 Film, Silicon Oxide Deposition Film / Co-
Thin film / linear low-density polyethylene resin layer / heat-sealable resin layer Next, using the liquid seasoning packaging laminate produced above, a three-way seal type plastic is produced by a di-roll filling and packaging machine. When a bag-making product is manufactured and a liquid seasoning is filled, and then the opening is heat-sealed to manufacture a packaged product, it has a high barrier property and deterioration of the barrier property is also recognized. In addition, it is also excellent in fragrance retention, and moreover, it is a laminer
Very good results with excellent strength were obtained.

Example 8 In Example 2 above, a laminate adhesive layer was formed on the coating thin film surface of the fragrance preserving primer composition, and then the laminate adhesive layer was formed. Instead of forming a heat-sealable resin layer composed of a co-extruded film having a thickness of 60 μm composed of linear low-density polyethylene and ethylene-α-olefin polymerized by using a metallocene catalyst on the layer surface, a fragrance A linear low-density polyethylene was used on the surface of a thin film coated with a hydrophilic primer composition, and while it was melt extruded to a thickness of 20 μm through an anchor coating agent, a linear low-density polyethylene was prepared in advance. Polyethylene and ethylene-α-olefin polymerized using a metallocene catalyst were used, and these were coextruded to a thickness of 30 μm to form a coextruded film having a thickness of 60 μm. A laminate for packaging a liquid seasoning according to the present invention having the following layer structure was produced in the same manner as in Example 1 except that the laminate was extruded and laminated. Biaxially stretched nylon 6 film / aluminum oxide deposition film / coating thin film / linear low-density polyethylene resin layer / heat-sealable resin layer Next, using the above-prepared liquid seasoning packaging laminate material , A three-way seal type plastic bag was manufactured by a di-roll filling and packaging machine, liquid seasoning was filled, and then the opening was heat-sealed to produce a packaged product. It has excellent barrier properties, no deterioration of the barrier properties is observed, and it is also excellent in fragrance retention.
Very good results with excellent strength were obtained.

Comparative Example 1 Thickness 20 formed by using chemical vapor deposition (CVD)
A 15 μm thick biaxially stretched nylon 6 film having a vapor deposition film of 0Å silicon oxide was formed on the surface of the vapor deposition film of silicon oxide having a thickness of 200Å of 7% of the same two-component curing type polyurethane resin as in Example 1 above. A laminate adhesive composed of an ethyl acetate and a toluene solution was used, and this was coated to a film thickness of 3 μm using a gravure roll coat method to form a laminate adhesive layer, Next, linear low-density polyethylene and an ethylene-α-olefin copolymer polymerized using a metallocene catalyst were used on the adhesive layer surface for lamination, and these were coextruded to a thickness of 30 μm. A heat-extruded film with a thickness of 60 μm.
A tosyllable resin layer was formed to produce a liquid seasoning packaging laminate having the following layer structure. Biaxially stretched nylon 6 film / silicon oxide vapor-deposited film / laminate adhesive layer / heat-sealable resin layer Using the liquid seasoning packaging laminate produced above, a Dunroll filling and packaging machine A three-way seal type plastic bag was manufactured by the above method, and the liquid seasoning was filled therein. Thereafter, the opening was heat-sealed to manufacture a filled packaged product.

Comparative Example 2 Thickness 20 formed by using physical vapor deposition (PVD)
Thickness 15μm with 0Å aluminum oxide film
Adhesion for lamination of 7% ethyl acetate of the same two-component curable polyurethane resin as in Example 2 above and a toluene solution on the surface of the vapor-deposited aluminum oxide film having a thickness of 200Å of the biaxially stretched nylon 6 film An agent is used, and this is coated by a gravure roll coat method to a film thickness of 3 μm to form an adhesive layer for laminate, and then, on the adhesive layer surface for laminate, Linear low density polyethylene,
An ethylene-α-olefin copolymer polymerized using a metallocene catalyst is used, and each of these has a thickness of 30 μm.
Was co-extruded to form a heat-sealable resin layer made of a co-extruded film having a thickness of 60 μm, and a liquid seasoning packaging laminate having the following layer structure was produced. Biaxially stretched nylon 6 film / aluminum oxide vapor deposition film / laminate adhesive layer / heat sealable resin layer Using the liquid seasoning packaging laminate produced above, a Dunroll filling and packaging machine A three-way seal type plastic bag was manufactured by the above method, and the liquid seasoning was filled therein. Thereafter, the opening was heat-sealed to manufacture a filled packaged product.

Experimental Example 1 Liquid-seasoning packaging laminates and liquid-seasoning packaging bags produced in Examples 1 to 8 above, and liquid seasoning packaging laminates produced in Comparative Examples 1 to 2 above. And the liquid seasoning packaging bag, Examples 1 to 8 have surfaces of the inorganic oxide thin film, the surface of the coating thin film, and the surface of the heat sealable resin layer having a thickness of 60 μm. In Comparative Examples 1 and 2, a laminate strength test and a tearability test were performed on the surface of the vapor-deposited film of inorganic oxide and the surface of the heat-sealable resin layer having a thickness of 60 μm. For the above-mentioned laminate strength test, a peeling tester (manufactured by Orientec Co., Ltd., model name, Tensilon universal testing machine) was used, and the sample was 15 mm wide, the peeling angle was 90 degrees, and the load cell was 5 k.
It was performed under the conditions of gf and a peeling speed of 50 mm / min. Further, in the tearability test, a notch of 5 mm was made on the edge of the laminated material, and a tear was made by hand, and the tearing feeling was evaluated. The results are shown in Table 1 below.

[0045] In Table 1 above, the view of the tearability means that ◯ means tearing without resistance, and x means that the base material and the heat-sealable resin layer tear apart and do not tear.

As shown in Table 1 above, the laminating strengths of Examples 1 to 8 are remarkably higher than those of Comparative Examples 1 and 2, so that the coating thin film is formed. It was found that the peel strength was improved. The tearability was also good. On the other hand, those of Comparative Examples 1 and 2 were not preferable because the laminate strength was not improved so much.

Experimental Example 2 Furthermore, the liquid seasoning packaging laminates produced in Examples 1 to 8 above and the liquid seasoning packaging laminates produced in Comparative Examples 1 to 2 were used. The following data was measured for the liquid seasoning packaging bag produced by making the above-mentioned bag or box. (1). Measurement of Oxygen Permeability This is measured under the conditions of temperature 23 ° C and humidity 90% RH in the United States,
The measurement was performed using a measuring machine [model name, OXTRAN] manufactured by MOCON. (2). Measurement of water vapor permeability This is a measuring instrument [model name, part number, manufactured by MOCON, USA under the conditions of a temperature of 40 ° C. and a humidity of 100% RH.
Matran]. The above measurement results are shown in Table 2 below.

[0048] In Table 2 above, the oxygen permeability is cm ³ / m ² / d
ay · 23 ° C. · 90% RH unit, and the water vapor permeability is g / m ² / day · 40 ° C. · 100% RH unit.

As is clear from the results shown in Table 2 above, the samples of Examples 1 to 8 were good in oxygen permeability and water vapor permeability, whereas in Comparative Examples 1 to 8.
Both of the two were inferior.

Experimental Example 3 The liquid seasoning packaging laminates produced in the above Examples 1 to 8 and the liquid seasoning packaging laminates produced in the above Comparative Examples 1 to 2 were used. A bag or a box is manufactured to produce a liquid seasoning packaging pouch, and then 10 cc of dressing (blue diso dressing) is placed in the liquid seasoning packaging pouch.
After filling and sealing, 250 pouch packages were manufactured, and then the pouch packages were placed in a pouch made of a packaging material laminated with aluminum foil, sealed, and stored at 37 ° C. for 2 days, The pouch was opened, and a sensory evaluation experiment was conducted by 5 panelists. The results are shown in Table 3 below.

[0051] In Table 3 above, the sensory evaluation points are almost odorless.
The following points were evaluated: a point, a slight odor, 3 points, and a considerable odor, 1 point, the total point, and the maximum was 25 points.

As is clear from Table 3 above, Example 1
Nos. 8 to 8 have excellent aroma retention properties and storage aptitude, while those of Comparative Examples 1 to 2 have poor aroma retention properties and lack in storage aptitude.

[0053]

As is apparent from the above description, the present invention focuses on a polyester resin having a high fragrance-retaining property, and one layer or two layers of a thin film of an inorganic oxide is formed on one surface of a base film.
A multi-layered film having at least two layers is provided, and further, a coating thin film is provided on the above-mentioned inorganic oxide thin film with a fragrance-preserving primer composition containing a polyester resin as a main component of a vehicle, and further, On the coating thin film, at least, a heat-sealing resin layer is laminated to form a laminated material,
Thus, the laminated material is used to form a bag or a box to produce a packaging bag, and then the packaging bag is filled with liquid or viscous contents such as a liquid seasoning. It has excellent transparency and high barrier property against oxygen gas or water vapor, and also permeates aroma components contained in the contents, and has excellent aroma retention to prevent odor leakage, etc. , Excellent puncture resistance, laminate strength, etc., and excellent preservability for liquid or viscous contents such as liquid seasonings, and without the occurrence of cracks during post-processing, extremely high post-processing Laminated material that has suitability, and has sufficient microwave suitability even when the packaged product is subjected to a microwave oven, and has suitability for filling and packaging various liquid seasonings as a packaging material, and a package using the same. That they can manufacture bags and the like Than it is.

[Brief description of drawings]

FIG. 1 is a schematic cross-sectional view showing a layer structure of a laminated material for liquid seasoning packaging according to the present invention.

FIG. 2 is a schematic cross-sectional view showing the layer structure of a laminated material for liquid seasoning packaging according to the present invention.

FIG. 3 is a schematic cross-sectional view showing the layer structure of a laminated material for liquid seasoning packaging according to the present invention.

FIG. 4 is a schematic perspective view showing a configuration of a bag for packaging liquid seasonings, which is formed or boxed using the laminated material for packaging liquid seasonings according to the present invention.

FIG. 5 is a schematic perspective view showing the configuration of a bag for packaging liquid seasonings, which is manufactured or boxed using the laminated material for packaging liquid seasonings according to the present invention.

FIG. 6 is a schematic configuration diagram showing an example of a roll-up type vapor deposition machine.

FIG. 7 is a schematic configuration diagram showing an example of a plasma chemical vapor deposition apparatus.

[Explanation of symbols]

1 Base film 2 Thin film of inorganic oxide 3 coating thin film 4 Heat-seal resin layer 5 Adhesive layer for laminate 5a Anchor-coating agent layer 6 Print pattern layer 7 seal part A Liquid laminate for packaging seasonings B Liquid seasoning laminates C Liquid seasoning packaging laminate D Three-sided seal type liquid seasoning packaging bag E Two-way seal type liquid seasoning packaging bag

Front page continuation (51) Int.Cl. ⁷ Identification code FI theme code (reference) C23C 16/40 C23C 16/40 (72) Inventor Hideaki Takahashi 1-1-1, Ichigayakacho, Shinjuku-ku, Tokyo Dai Nippon printing Co., Ltd. in the F-term (reference) 3E086 AB01 AD01 BA04 BA15 BA24 BA40 BB02 BB05 BB22 CA01 4F100 AA17B AA17C AA19B AA19C AA20B AA20C AK41D AK42G AK46A AK51D AK51G AR00E AT00A BA05 BA07 BA10A BA10E CB00 EH66B EH66C EJ38A GB16 HB31D JD03 JD04 JK01 JK02G JK10 JL00 JL00D JL12 JL12E JM02B JM02C YY00G 4K029 AA11 AA25 BA43 BA44 BA46 BB02 BC08 BD00 CA01 4K030 BA42 BA44 CA07 CA12 HA04 LA01 LA24

Claims (13)

[Claims] 1. A substrate film is provided on one surface thereof with a multilayer film of one or more inorganic oxide thin films, and a polyester resin is used as a vehicle on the inorganic oxide thin film. A liquid comprising a coating thin film formed of a fragrance-preserving primer composition as a main component, and at least a heat-sealing resin layer laminated on the coating thin film. Laminated material for seasoning packaging. 2. The laminated material for liquid seasoning packaging according to claim 1, wherein the base film is a biaxially stretched nylon film or a biaxially stretched polyethylene terephthalate film. 3. The laminate for packaging a liquid seasoning according to any one of claims 1 and 2, wherein the thin film of the inorganic oxide comprises one layer or two or more layers of a vapor deposition film of the inorganic oxide. 4. The liquid seasoning according to any one of claims 1 to 3, wherein the thin film of inorganic oxide comprises one layer or two or more layers of a vapor deposition film of inorganic oxide prepared by physical vapor deposition. Laminated material for food packaging. 5. The liquid seasoning according to any one of claims 1 to 3, wherein the thin film of inorganic oxide comprises one layer or two or more layers of a vapor deposition film of inorganic oxide formed by a chemical vapor deposition method. Laminated material for food packaging. 6. The inorganic oxide thin film comprises at least two layers of a vapor deposited film of an inorganic oxide formed by physical vapor deposition and chemical vapor deposition, according to any one of claims 1 to 3. A laminated material for packaging liquid seasonings. 7. The liquid seasoning packaging laminate according to any one of claims 1 to 6, wherein the vapor deposition film of inorganic oxide comprises a vapor deposition film of silicon oxide or aluminum oxide. 8. The fragrance-imparting primer composition according to claim 1, wherein the fragrance-imparting primer composition comprises polyester polyol as a main component of the vehicle and further an isocyanate compound. Item 1. A laminated material for packaging a liquid seasoning according to items 1 to 7. 9. The laminated material for liquid seasoning packaging according to any one of claims 1 to 8, wherein a printed pattern layer is further provided on the coating thin film. 10. An adhesive or anchor coat for laminating between the coating thin film and the heat-sealable resin layer.
The laminated material for packaging a liquid seasoning according to any one of claims 1 to 9, wherein the laminated material is laminated via a coating agent layer. 11. The adhesive layer for laminate comprises an adhesive layer for laminate which is formed into a film by a curing reaction between polyester polyol or polyether polyol and a polyfunctional isocyanate. The laminated material for packaging a liquid seasoning according to claim 10, which is characterized by the above. 12. The adhesive layer for laminate is JIS K
23 ° C, 50% RH with No. 4 dumbbell according to 6301
300 mm / min. The laminated material for liquid seasoning packaging according to claim 11, having a tensile elongation of 300% to 550% measured under the speed condition of. 13. A substrate film is provided on one surface thereof with a multilayer film of one layer or two or more layers of a thin film of an inorganic oxide, and
On the thin film of the inorganic oxide, a polyester-based resin as a main component of the vehicle was coated with a perfuming primer composition.
A coating thin film is provided, and a liquid seasoning packaging laminate having a structure in which at least a heat-sealing resin layer is laminated on the coating thin film is used, and the liquid seasoning is laminated in a box or a box. A bag for packaging a liquid seasoning characterized by being formed into a bag.