JP4028259B2 - Gas barrier vapor deposition laminate - Google Patents

Gas barrier vapor deposition laminate Download PDF

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JP4028259B2
JP4028259B2 JP2002059652A JP2002059652A JP4028259B2 JP 4028259 B2 JP4028259 B2 JP 4028259B2 JP 2002059652 A JP2002059652 A JP 2002059652A JP 2002059652 A JP2002059652 A JP 2002059652A JP 4028259 B2 JP4028259 B2 JP 4028259B2
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thin film
vapor deposition
metal
deposited
gas barrier
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JP2003251731A (en
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好弘 岸本
茂樹 松井
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大日本印刷株式会社
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Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a gas barrier vapor-deposited laminate, more specifically, excellent in tight adhesion between each layer, and excellent in gas barrier properties against moisture, moisture, etc., mainly useful as a packaging material. The present invention relates to a gas barrier vapor-deposited laminate.
[0002]
[Prior art]
Conventionally, various packaging materials have been developed and proposed for filling and packaging various articles such as foods and drinks, pharmaceuticals, cosmetics, detergents, miscellaneous goods, and the like.
Thus, as one of them, there is a barrier material against oxygen gas or water vapor, which is always required when manufacturing packaging containers. For this reason, various materials have been conventionally used. Barrier materials consisting of forms have been developed and proposed.
At present, aluminum foil is used as the most common barrier material, and an aluminum vapor deposited film obtained by vapor-depositing a metal element such as aluminum on one side of a plastic film is also used as a general barrier material.
By the way, in recent years, in the barrier material, as a material for further improving the performance, for example, there is a transparent barrier material having a structure in which a vapor-deposited film of a metal oxide such as silicon oxide or aluminum oxide is provided on one side of a plastic film Developed and proposed.
Furthermore, in the transparent barrier material composed of the above-described aluminum vapor-deposited film or a metal oxide vapor-deposited film such as silicon oxide and aluminum oxide, as a protective film, on the vapor-deposited film, A barrier material having a structure provided with a vapor-deposited thin film of an organic compound has also been developed and proposed.
[0003]
[Problems to be solved by the invention]
However, in the barrier material as described above, the aluminum foil is a material that is extremely excellent in barrier properties and the like, but has problems such as poor transparency and poor environmental response. .
Next, in the transparent barrier material having a structure provided with the above-described aluminum vapor-deposited film or a metal oxide vapor-deposited film such as silicon oxide or aluminum oxide, the barrier property is a single plastic as a substrate. Although it is significantly improved as compared with the film, it should not be far from that of the aluminum foil.
For example, an unstretched polypropylene film (CPP) or an aluminum deposited film obtained by depositing aluminum on a polyethylene film or the like is inferior in barrier properties, particularly oxygen gas barrier properties, and specifically, an unstretched polypropylene film (CPP) having a thickness of 25 μm. In the aluminum vapor deposition film in which aluminum is vapor-deposited, the oxygen permeability is generally about 30 cc.
Moreover, in the barrier material composed of a vapor deposition film and a vapor deposition thin film of an organic compound as the protective film, the barrier property against oxygen gas, water vapor, etc. is not improved. However, it often causes a problem in the adhesion between the plastic film as the substrate and the deposited film. If the adhesion of the deposited film to the plastic film is inferior, the adhesion strength decreases and a peeling phenomenon occurs between the layers. In addition, there is a problem that the barrier property against moisture, moisture resistance and the like against oxygen gas and water vapor are remarkably impaired.
Therefore, the present invention is excellent in adhesion strength between a plastic film as a substrate and a vapor deposition film, and excellent in gas barrier properties, moisture resistance, etc. against oxygen gas, water vapor, etc., and is mainly a barrier material useful as a packaging material. Is to provide.
[0004]
[Means for Solving the Problems]
As a result of various studies to solve the above problems, the present inventor has provided a primer coat layer made of an organic compound on the surface of a plastic base material as a base material. The heat resistance is improved, and the smoothness is improved by covering the unevenness of the surface, and the surface wettability, affinity, etc. are also improved, and the tight adhesion to the deposited thin film layer of metal or metal oxide First, a primer coat layer made of an organic compound is provided on at least one surface of the plastic substrate, and then a metal or metal oxide layer is formed on the surface of the primer coat layer made of the organic compound. When a vapor-deposited laminate was manufactured by sequentially providing a vapor-deposited thin film layer of an organic compound on the surface of the vapor-deposited thin film layer of the metal or metal oxide, a plastic substrate and a metal or metal acid were produced. The deposited thin film layer of the object is firmly and closely bonded through the primer coat layer made of an organic compound, and there is no phenomenon such as delamination between the layers. Further, the oxygen permeability, water vapor permeability, etc. The present invention has been completed by finding that an excellent and extremely useful barrier vapor deposition laminate can be produced.
[0005]
That is, the present invention is characterized in that a primer coat layer made of an organic compound, a metal or metal oxide thin film layer, and an organic compound thin film layer are sequentially provided on at least one surface of a plastic substrate. The present invention relates to a gas barrier vapor deposition laminate.
[0006]
DETAILED DESCRIPTION OF THE INVENTION
The above-described present invention will be described in more detail below.
First, an example of the configuration of the gas barrier vapor deposition laminate according to the present invention will be described with reference to the drawings. FIG. 1 is a schematic diagram showing an example of the layer configuration of the gas barrier vapor deposition laminate according to the present invention. FIG. 2 is a schematic cross-sectional view showing an example of the structure of the gas barrier vapor-deposited laminate according to the present invention.
[0007]
An example of the gas barrier vapor-deposited laminate according to the present invention will be described below. As shown in FIG. 1, the gas barrier vapor-deposited laminate 1 according to the present invention has at least a plastic substrate 2 as a basic configuration. At least one primer coat layer 3 made of an organic compound, a metal or metal oxide thin film layer 4 and an organic compound thin film layer 5 are sequentially provided on one surface.
Thus, in the gas barrier vapor deposition laminate according to the present invention having the above-described configuration, first, by providing a primer coat layer of an organic compound on the surface of the plastic substrate, the plastic substrate itself This improves the heat resistance of the plastic substrate and prevents thermal deterioration of the plastic substrate when the metal or metal oxide thin film layer is formed.
In the present invention, by providing a primer coat layer of an organic compound on the surface of the plastic substrate, the unevenness of the surface of the plastic substrate is covered to improve the smoothness, and the surface is wetted. It improves the property, affinity, etc., improves the tight adhesion with the thin film layer of metal or metal oxide, strengthens the tight adhesion strength, and prevents the delamination and the like.
In the present invention, the organic compound thin film layer 5 is provided on the metal or metal oxide thin film layer 4 so that the organic compound thin film layer 5 protects the metal or metal oxide thin film layer 4. For example, the surface of the thin film layer 4 of metal or metal oxide has protective effects such as damage and corrosion.
[0008]
Next, in the present invention, the method for producing the gas barrier vapor-deposited laminate according to the present invention will be described with reference to a take-up vacuum vapor deposition machine as an example. As shown in FIG. The plastic substrate 2 provided with a primer coat layer (3) made of an organic compound in advance in the vacuum chamber 12 of the vapor deposition apparatus 11 from the unwinding roll 13 is guided to the guide rollers 14 and 15. Then, the cooled coating drum 16 is guided to the cooled coating drum 16, and first, on the coating drum 16, a primer coating layer made of an organic compound previously provided on the plastic substrate 2 ( 3) The metal or metal oxide 18 heated as an evaporation source by the crucible 17 is evaporated on the surface of 3) (arrow), and if necessary, oxygen gas or the like is supplied from an oxygen outlet or the like (not shown) if necessary. The metal or metal oxide vapor-deposited thin film layer (on the surface of the primer coat layer (3) of the organic compound formed in advance on the surface of the plastic substrate 2 through the masks 19 and 19). 4) is formed into a film, and then the plastic substrate 2 on which the metal or metal oxide vapor-deposited thin film layer (4) is formed is wound up through the guide rolls 15 'and 14'. At the time of winding the film 22, the organic compound 21 heated as a vapor deposition source in the crucible 20 is evaporated between the guide roll 15 ′ and the coating drum 16 (arrow), and is applied to the surface of the plastic substrate 2. An organic compound vapor-deposited thin film layer (5) is further formed on the organic compound primer coat layer (3) and the metal or metal oxide vapor-deposited thin film layer (4). On at least one surface of the material 2, At least, the gas barrier property according to the present invention, in which a primer coat layer (3) by an organic compound, a metal or metal oxide thin film layer (4), and an organic compound thin film layer (5) are sequentially provided. A vapor deposition laminated body can be manufactured.
[0009]
In the method for producing a gas barrier vapor-deposited laminate according to the present invention as described above, a primer coat layer made of an organic compound is previously formed on the surface of a plastic substrate, as is apparent from the above description, and the primer is formed. -A thin film layer of metal or metal oxide and a vapor deposited thin film layer of an organic compound are continuously deposited on the surface of the coat layer in the same chamber using a vacuum vapor deposition machine or the like. To increase productivity and the like.
Specifically, in the present invention, the surface of the primer coat layer of a plastic substrate provided with a primer coat layer of an organic compound in advance in the same chamber such as a vacuum vapor deposition machine, A metal or metal oxide thin film layer is formed by vapor deposition or the like. Further, immediately after the metal or metal oxide thin film layer is formed by vapor deposition or the like, an organic layer is formed on the surface of the metal or metal oxide thin film layer. The productivity is increased by forming the compound thin film layer by vapor deposition or the like.
In particular, in the present invention, when the metal or metal oxide thin film layer and the organic compound thin film layer are sequentially formed, the surface of the metal or metal oxide thin film layer is free of other foreign matters such as guide lines. -It is preferable to avoid contact with the surface of a metal or the like, and a vapor-deposited thin film of the following organic compound is directly formed on the surface of the thin film layer of metal or metal oxide immediately after vapor deposition, and close adhesion between the layers It is preferable to improve the protective thin film properties.
That is, in the above, when the organic compound thin film layer is formed, the surface of the metal or metal oxide thin film layer is prevented from coming into contact with, for example, the surface of the guide roll or the like. It has the advantage that generation | occurrence | production can be prevented reliably.
The above exemplification is an example of the gas barrier vapor-deposited laminate according to the present invention or the production method thereof, and it goes without saying that the present invention is not limited thereto. .
[0010]
Next, in the present invention, the gas barrier vapor deposition laminate according to the present invention as described above, or materials used in the production method thereof, the production method thereof, etc. will be described. First, the present invention relates to the present invention. The plastic substrate constituting the gas barrier vapor-deposited laminate may be any plastic film or sheet that holds the primer coat layer and can hold each vapor-deposited thin film layer. For example, polyolefin resins such as polyethylene, polypropylene, polybutene, (meth) acrylic resins, polyvinyl chloride resins, polystyrene resins, polyvinylidene chloride resins, ethylene-vinyl acetate copolymer ken , Polyvinyl alcohol, polycarbonate resin, fluorine resin, polyvinyl acetate resin, Seta - Le resins, polyester resins, polyamide resins, and other various kinds of transparent resin film or sheet - may be used and.
These resin films or sheets may be uniaxially or biaxially stretched, and the thickness is about 10 to 200 μm, preferably about 10 to 100 μm.
The resin film or sheet may be optionally subjected to pretreatment such as corona discharge treatment, ozone treatment or plasma treatment, if necessary.
[0011]
Next, in the present invention, examples of the organic compound forming the primer coat layer made of the organic compound constituting the gas barrier vapor deposition laminate according to the present invention include, for example, polyurethane resins, polyester resins, polyamide resins. , Epoxy resin, phenol resin, polyvinyl acetate resin, vinyl chloride-vinyl acetate copolymer, acid-modified polyolefin resin, (meth) acrylic resin, polybutadiene resin, rubber compound, petroleum resin , Alkyl titanate compounds, polyethyleneimine compounds, isocyanate compounds, starches, caseins, gum arabic, cellulose derivatives, waxes, and other resins or prepolymers or monomers thereof. Can be used.
In the present invention, as the above-mentioned resin or its prepolymer or monomer, any one of one-component curable type or two-component curable type can be used.
Thus, in the present invention, one or more mixtures of the above-mentioned resins or prepolymers or monomers thereof are used as the main component of the vehicle, and if necessary, for example, various stabilizers, Additives such as curing agents or crosslinking agents, fillers, etc. are arbitrarily added, and kneaded sufficiently with a solvent, a diluent, etc. to prepare a coating agent composition, and the coating agent composition is This is applied to the surface of the plastic substrate by a coating method such as a roll coating method, a gravure coating method, a spray coating method, an air knife coating method, a kiss coating method, etc. By coating, a primer coat layer made of an organic compound can be formed.
In the present invention, the film thickness of the primer coat layer made of the organic compound is preferably about 500 to 5000 mm.
In the present invention, as the above-mentioned coating method, it is most desirable to use a gravure coating method from the viewpoints of productivity, film thickness uniformity, and the like.
[0012]
Next, in the present invention, the metal or metal oxide forming the thin film layer of the metal or metal oxide constituting the gas barrier vapor deposition laminate according to the present invention is basically formed by vapor deposition or the like. Alternatively, any material can be used as long as it can form a thin film layer in which a metal oxide is made amorphous. 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), or other metals, or Metal oxides can be used.
Thus, metal oxides such as aluminum, silicon or aluminum can be cited as suitable for packaging materials.
In the present invention, the metal oxide is represented by, for example, SiO, such as silicon oxide, aluminum oxide, magnesium oxide, etc. X AlO X , MgO X MO etc. X (In the formula, M represents a metal element, and the value of X varies depending on the metal element.)
Thus, the range of the value of X in the above formula is 0-2 for silicon (Si), 0-1.5 for aluminum (Al), 0-1 for magnesium (Mg), 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, and boron (B) is 0. -1,5, titanium (Ti) is 0-2, lead (Pb) is 0-1, zirconium (Zr) is 0-2, yttrium (Y) is 0-1.5. Can take.
In the above, when X = 0, it is a complete metal, and the upper limit of the range of X is a completely oxidized value.
In the present invention, as a packaging material, generally, silicon (Si) and aluminum (Al) other than silicon (Si) are rarely used, and silicon (Si) is 1.0 to 2.0, aluminum (Al ) Having a value in the range of 0.5 to 1.5 can be used.
[0013]
Next, in the present invention, the organic compound forming the organic compound thin film constituting the gas barrier vapor-deposited laminate according to the present invention is a compound mainly composed of carbon and hydrogen, and further, for example, oxygen Further, it may contain an element such as nitrogen, and may further contain a trace amount of a metal element, and further, an organic compound that is liquid or solid at room temperature can be used for forming a deposited thin film layer.
Examples of the organic compound include natural or synthetic resins, natural or synthetic rubbers, mixtures of one or more natural or synthetic waxes, and mixtures of one or more lubricants. be able to.
Specifically, for example, polyolefin resin such as polyethylene resin or polypropylene resin, methylpentene resin, polybutene resin, polystyrene resin, poly (meth) acrylic resin, polyacrylonitrile resin, polycarbonate -Resin, phenol resin, furan resin, ketone resin, xylene resin, melamine resin, urea resin, aniline resin, polyester resin, polyamide resin, epoxy resin, etc. Synthetic resins, natural resins such as rosin, shellac, etc., ethylene-propylene rubber, butyl rubber, nitrile rubber, acrylic rubber, silicone rubber, etc., synthetic rubbers, natural rubbers such as raw rubber, paraffin wax, fine Crystal wax, candelilla wax, carnauba wax, Monta Natural or synthetic waxes such as wax, polyolefin wax, microcrystalline wax, etc., silicone oil, fluorine oil, polyalkylnaphthalene oil, polyalkylphthalate oil polyphenyl ether oil, petroleum fraction, Lubricants such as mineral oil and others can be used.
In this invention, said organic compound can be used individually or in mixture of 2 or more types.
[0014]
In the above, one kind or a mixture of two or more kinds of lubricants can be used alone as an organic compound constituting the organic compound thin film layer. However, in the present invention, natural or synthetic resins, natural or synthetic resins can be used. An organic compound thin film is formed by forming a deposited film of an organic compound composition obtained by adding one or more mixtures of lubricants to one or more mixtures of rubber or natural or synthetic waxes. It is desirable to constitute the layer.
Thus, by using the lubricant as described above, it is possible to improve the slipperiness of the organic compound thin film layer, and particularly when the gas barrier vapor deposition laminate according to the present invention is wound up, It has the advantage that generation | occurrence | production etc. can be prevented.
[0015]
Next, in the present invention, a primer coat layer made of an organic compound is provided in advance on at least one surface of the plastic substrate, and then a metal or metal oxide thin film layer, and a second organic compound thin film As a method of sequentially providing the layers, for example, a physical vapor deposition method (Physical Vapor Deposition method, PVD method) such as a vacuum deposition method, a sputtering method, an ion plating method, a plasma chemical vapor deposition method, a thermochemistry, or the like. A chemical vapor deposition method (Chemical Vapor Deposition method, CVD method) such as a vapor deposition method or a photochemical vapor deposition method can be given.
Of course, in the present invention, a part can be performed by a physical vapor deposition method such as a vacuum deposition method, and the other can be performed by a chemical vapor deposition method such as a plasma chemical vapor deposition method.
In the present invention, a resistance heating method, an induction heating method, an electron beam heating method, or the like can be appropriately selected and employed as a vapor deposition method in the above vacuum vapor deposition method.
Further, in the present invention, when forming a thin film layer of metal or metal oxide, the above-described plasma chemical vapor deposition method is employed, for example, plasma using organosilicon compound gas such as tetramethylenedisiloxane or hexamethylenedisiloxane as a raw material. Activated chemical vapor deposition can be performed.
[0016]
By the way, in this invention, as thickness of each layer, such as a thin film layer of a metal or a metal oxide, and a 2nd organic compound thin film layer, as a thickness of a thin film layer of a metal or a metal oxide, it is first used. Depending on the type of metal or metal oxide, etc., it is desirable to select and form the layer arbitrarily within a range of, for example, 50 to 3000 mm, preferably 100 to 1000 mm.
In the present invention, the thickness of the organic compound thin film layer is about 500 to 5,000 mm, preferably about 1,000 to 2,000 mm.
Next, in the present invention, the thin film layer of metal or metal oxide may be in the form of a laminate in which not only one layer but also two or more layers are laminated, and the metal used or the metal oxide As a thing, it can also be used by the 1 type, or 2 or more types of mixture, and can also comprise the thin film layer by the material mixed by the dissimilar material.
[0017]
As is clear from the above description, the present invention sequentially forms a primer coat layer made of an organic compound, a metal or metal oxide thin film layer, and an organic compound thin film layer on at least one surface of a plastic substrate. It is related with the gas-barrier vapor deposition laminated body characterized by being provided in.
Thus, in the gas barrier vapor deposition laminate according to the present invention, the plastic base material and the metal or metal oxide vapor deposition thin film layer are firmly and tightly bonded via the primer coat layer made of an organic compound. No phenomenon such as delamination is observed between the layers, and the deposited thin film layer of the organic compound acts as a protective thin film for protecting the deposited thin film layer of the metal or metal oxide. Gas barrier properties that are not obtained with conventional gas barrier films made of vapor-deposited films. It is useful as a packaging material for producing various packaging containers as a gas barrier material.
In addition, the gas barrier vapor-deposited laminate according to the present invention is provided with a thin film layer of an organic compound on both surfaces of a vapor-deposited thin film layer of a metal or metal oxide that lacks flexibility. Acts as a protective layer for the vapor-deposited thin film layer. For example, it is a metal or metal oxide vapor-deposited thin film layer in rewinding between manufacturing processes, slitting, and post-processing such as printing, lamination, bag making, etc. No cracks or the like occur in the film, and it is extremely excellent in its production or post-processing suitability. Furthermore, in this invention, since each thin film layer is formed continuously by vapor deposition etc., the productivity is improved.
[0018]
The gas barrier vapor-deposited laminate according to the present invention produced as described above includes, for example, packaging materials constituting packaging containers such as resin films, paper base materials, metal materials, synthetic paper, cellophane, etc. In any combination, for example, various laminates can be produced by laminating by an ordinary lamination method, and packaging containers suitable for filling and packaging various articles can be produced.
Specifically, as the resin film, 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, acid-modified polyolefin resin, methylpentene polymer, polybutene resin, polyvinyl chloride resin, polyvinyl acetate resin , Polyvinylidene chloride resin, vinyl chloride-vinylidene chloride copolymer, poly (meth) acrylic resin, polyacrylonitrile resin, polystyrene resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene- Styrene copolymer (AB Resin), polyester resin, polyamide resin, polycarbonate resin, polyvinyl alcohol resin, saponified ethylene-vinyl acetate copolymer, fluorine resin, diene resin, polyacetal resin A resin, polyurethane resin, nitrocellulose, or other known resin film or sheet may be arbitrarily selected and used.
In the present invention, the above-described film or sheet may be any of unstretched, uniaxially or biaxially stretched.
The thickness is arbitrary, but can be selected from a range of several μm to 300 μm.
Further, in the present invention, the film or sheet may be a film having any property such as extrusion film formation, inflation film formation, and coating film.
In addition, in the above, as the paper base, for example, a paper base such as a strong sized bleached or unbleached paper, or a pure white roll paper, kraft paper, paperboard, processed paper, or the like is used. can do.
In the above, the paper substrate constituting the paper layer has a basis weight of about 80 to 600 g / m. 2 , Preferably a basis weight of about 100 to 450 g / m 2 It is desirable to use the one of the order.
[0019]
Next, in the present invention described above, a method for producing a laminate using the above materials will be described. As such a method, a method for laminating a normal packaging material, for example, wet lamination is used. , Dry lamination method, solventless dry lamination method, extrusion lamination method, T-die extrusion molding method, co-extrusion lamination method, inflation method, co-extrusion inflation method, etc. be able to.
Thus, in the present invention, when performing the above lamination, if necessary, pretreatment such as corona treatment, ozone treatment, frame treatment, etc. can be applied to the film. , Polyester-based, isocyanate-based (urethane-based), polyethyleneimine-based, polybutadiene-based, organic titanium-based anchor coating agents, or polyurethane-based, polyacrylic-based, polyester-based, epoxy-based, polyvinyl acetate-based Well-known anchor coating agents, adhesives, etc., such as adhesives for laminating, etc. can be used.
[0020]
Next, in the present invention, a method for making bags or boxes using the laminate as described above will be described. For example, in the case where the packaging container is a flexible packaging bag made of a plastic film or the like, the above method is used. The inner layer of the heat-seal resin layer is made to face each other and folded, or two of them are overlapped, and the peripheral edge of the laminate is heated. -A bag body can be constructed by providing a seal portion.
Thus, as the bag making method, the above laminated body is folded with the inner layer surfaces facing each other, or the two sheets are overlapped, and the peripheral edge of the outer periphery is, for example, a side sheet. Seal type, two-sided seal type, three-sided seal type, four-sided seal type, envelope-sealed seal type, jointed seal type (pillar seal type), pleated seal type The various types of packaging containers according to the present invention can be manufactured by heat sealing in the form of a heat sealing such as a flat bottom sealing type, a square bottom sealing type, or the like.
In addition, for example, a self-supporting packaging bag (standing pouch) or the like can be manufactured, and in the present invention, a laminated tube container or the like can also be manufactured using the above laminated material. .
In the above, as the heat seal method, for example, a bar seal, a rotary roll seal, a belt seal, an impulse seal, a high frequency seal, an ultrasonic seal and the like are known. It can be done by the method.
In the present invention, a spout such as a one-piece type, a two-piece type, or the like, or a zipper for opening and closing can be arbitrarily attached to the packaging container as described above.
[0021]
Next, in the case of a liquid-filled paper container including a paper base material as a packaging container, for example, as a laminated material, a laminated material in which a paper base material is laminated is manufactured, and a blank plate for manufacturing a desired paper container is prepared from this. After that, the body, bottom, head, etc. can be boxed by using the blank plate, and for example, a brick type, flat type or gable top type liquid paper container can be manufactured. .
Further, the shape can be any of a rectangular container, a cylindrical paper can such as a round shape, and the like.
[0022]
In the present invention, the packaging container produced as described above is excellent in transparency, gas barrier properties against oxygen, water vapor and the like, impact resistance, etc., and further, laminating, printing, bag making or box making. It is excellent as a barrier film by preventing the peeling of the deposited thin film as a barrier film, preventing the occurrence of thermal cracks, and preventing its deterioration. Demonstrate resistance, for example, excellent in packing and storage suitability for various articles such as foods and drinks, pharmaceuticals, detergents, shampoos, oils, toothpastes, adhesives, adhesives, and other chemicals and cosmetics, etc. It is what.
[0023]
【Example】
Example 1
A primer coat layer having a thickness of 1300 mm was formed on one side of a 25 μm-thick cast polypropylene film using the gravure coat method under the following conditions.
(Coating agent composition):
Main agent: nitrified cotton / polyurethane resin (solid content 25%)
Curing agent: Isocyanate compound (solid content 75%)
Mixing ratio; main agent: curing agent = 100: 5
Solvent; ethyl acetate
Next, on the surface of the primer coat layer of the cast polypropylene film on which the primer coat layer is formed as described above, an aluminum film having a thickness of 200 mm is deposited using an electron beam type vacuum deposition method under the following conditions. A film was formed, and thereafter, a synthetic wax vapor deposition thin film having a thickness of 2000 mm was continuously formed in the same chamber to produce a gas barrier vapor deposition laminate according to the present invention.
(Deposition conditions):
Degree of vacuum in winding chamber, 2 × 10 -2 mbar
Degree of vacuum in the deposition chamber 2 × 10 -Four mbar
Film speed: 200m / min
[0024]
Example 2
A primer coat layer was formed on one side of a 12 μm thick biaxially stretched polyethylene terephthalate film in the same manner as in Example 1 above.
Next, on the surface of the primer coat layer of the biaxially stretched polyethylene terephthalate film on which the primer coat layer was formed as described above, using a plasma chemical vapor deposition machine, the following film transfer speed was 200 m / min. Two layers were successively deposited in the same chamber.
First, using a plasma chemical vapor deposition method, a silicon oxide thin film having a thickness of 150 mm is formed from hexamethyldisiloxane as a raw material, and thereafter, a synthetic wax having a thickness of 2000 mm is continuously deposited in the same chamber. A thin film was formed to produce a gas barrier vapor deposition laminate according to the present invention.
[0025]
Example 3
A primer coat layer was formed on one side of a 12 μm thick biaxially stretched polyethylene terephthalate film in the same manner as in Example 1 above.
Next, the electron beam heating method is used on the primer coat layer surface of the biaxially stretched polyethylene terephthalate film on which the primer coat layer is formed as described above, and aluminum is used as a deposition source. Then, while supplying oxygen gas, an aluminum oxide vapor-deposited thin film layer having a thickness of 200 mm is formed, and thereafter, a synthetic wax vapor-deposited thin film having a thickness of 2000 mm is continuously formed in the same chamber. A gas barrier vapor deposition laminate according to the present invention was produced.
(Deposition conditions):
Degree of vacuum in winding chamber, 2 × 10 -2 mbar
Degree of vacuum in the deposition chamber 2 × 10 -Four mbar
Film speed: 400m / min
[0026]
Example 4
A primer coat layer having a thickness of 1300 mm was formed on one side of a 25 μm-thick cast polypropylene film using the gravure coat method under the following conditions.
(Coating agent composition):
Main agent: Saturated polyester resin (solid content 30%)
Curing agent: isocyanate compound (solid content 70%)
Mixing ratio; main agent: curing agent = 50: 50
Solvent; ethyl acetate
Next, on the surface of the primer coat layer of the cast polypropylene film on which the primer coat layer is formed as described above, an aluminum film having a thickness of 500 mm is deposited using an electron beam type vacuum deposition method under the following conditions. A film was formed, and thereafter, a synthetic wax vapor deposition thin film having a thickness of 2000 mm was continuously formed in the same chamber to produce a gas barrier vapor deposition laminate according to the present invention.
(Deposition conditions):
Degree of vacuum in winding chamber, 2 × 10 -2 mbar
Degree of vacuum in the deposition chamber 2 × 10 -Four mbar
Film speed: 200m / min
[0027]
Example 5
A primer coat layer was formed on one side of a 12 μm thick biaxially stretched polyethylene terephthalate film in the same manner as in Example 4 above.
Next, on the surface of the primer coat layer of the biaxially stretched polyethylene terephthalate film on which the primer coat layer was formed as described above, using a plasma chemical vapor deposition machine, the following film transfer speed was 200 m / min. Two layers were successively deposited in the same chamber.
First, using a plasma chemical vapor deposition method, a silicon oxide thin film having a thickness of 150 mm is formed from hexamethyldisiloxane as a raw material, and thereafter, a synthetic wax having a thickness of 2000 mm is continuously deposited in the same chamber. A thin film was formed to produce a gas barrier vapor deposition laminate according to the present invention.
[0028]
Example 6
A primer coat layer was formed on one side of a 12 μm thick biaxially stretched polyethylene terephthalate film in the same manner as in Example 4 above.
Next, the electron beam heating method is used on the primer coat layer surface of the biaxially stretched polyethylene terephthalate film on which the primer coat layer is formed as described above, and aluminum is used as a deposition source. Then, while supplying oxygen gas, an aluminum oxide vapor-deposited thin film layer having a thickness of 200 mm is formed, and thereafter, a synthetic wax vapor-deposited thin film having a thickness of 2000 mm is continuously formed in the same chamber. A gas barrier vapor deposition laminate according to the present invention was produced.
(Deposition conditions):
Degree of vacuum in winding chamber, 2 × 10 -2 mbar
Degree of vacuum in the deposition chamber 2 × 10 -Four mbar
Film speed: 400m / min
[0029]
Comparative Example 1
A 200 μm thick aluminum vapor deposition thin film was formed on one side of a cast polypropylene film having a thickness of 25 μm by using an electron beam heating method under the same conditions as in Example 1 above using a vacuum vapor deposition machine, A vapor deposition thin film of synthetic wax having a thickness of 2000 mm was continuously formed in the same chamber to produce a gas barrier vapor deposition laminate.
[0030]
Comparative Example 2
A 200 μm thick aluminum vapor deposition film was formed on one side of a 25 μm thick cast polypropylene film under the same conditions as in Example 1 using an electron beam type vacuum vapor deposition method, and gas barrier vapor deposition was performed. A laminate was produced.
[0031]
Comparative Example 3
The following two layers were continuously deposited on one side of a 12 μm thick biaxially stretched polyethylene terephthalate film using a plasma chemical vapor deposition machine at a film transport speed of 200 m / min in the same chamber.
First, using a plasma chemical vapor deposition method, a silicon oxide thin film having a thickness of 150 mm is formed from hexamethyldisiloxane as a raw material, and thereafter, a synthetic wax having a thickness of 2000 mm is continuously deposited in the same chamber. A thin film was formed to produce a gas barrier vapor deposition laminate.
[0032]
Comparative Example 4
Using a vacuum vapor deposition machine on one side of a 12 μm thick biaxially stretched polyethylene terephthalate film, using an electron beam heating system under the following conditions, while using aluminum as a deposition source and supplying oxygen gas Then, a vapor-deposited thin film layer of aluminum oxide having a thickness of 200 mm was formed, and then, a vapor-deposited thin film of synthetic wax having a thickness of 2000 mm was continuously formed in the same chamber to produce a gas barrier vapor-deposited laminate. .
(Deposition conditions):
Degree of vacuum in winding chamber, 2 × 10 -2 mbar
Degree of vacuum in the deposition chamber 2 × 10 -Four mbar
Film speed: 400m / min
[0033]
Experimental example 1
The oxygen permeability and water vapor permeability of the gas barrier vapor-deposited laminate according to the present invention produced in Examples 1 to 6 and the gas barrier vapor-deposited laminate produced in Comparative Examples 1 to 4 were measured.
(1). Measurement of oxygen permeability
Measurement was carried out using a measuring instrument (model name, OXTRAN 2/20) manufactured by MOCON, USA under the conditions of a temperature of 23 ° C. and a humidity of 90% RH.
(2). Measurement of water vapor transmission rate
The measurement was carried out using a measuring instrument (model name, Permatran 3/31) manufactured by MOCON, USA, under conditions of a temperature of 37.8 ° C. and a humidity of 100% RH.
The results measured above are shown in Table 1 below.
[0034]
[Table 1]
[0035]
As is clear from the results shown in Table 1, the gas barrier vapor-deposited laminate according to the present invention was found to be excellent in oxygen permeability and water vapor permeability and useful as a gas barrier material.
[0036]
Experimental example 2
Next, the gas barrier vapor-deposited laminate according to the present invention produced in Examples 2, 3, 5 and 6 above and the gas barrier vapor-deposited laminate produced in Comparative Examples 3 and 4 were used, and the vapor-deposited thin film surface thereof A biaxially stretched nylon film having a thickness of 15 μm is laminated using a urethane adhesive, and the biaxially stretched nylon film is laminated on the surface of the biaxially stretched nylon film in the same manner as described above. An unstretched polypropylene film having a thickness of 30 μm was bonded to produce a laminate.
Subsequently, the gas barrier vapor-deposited laminate according to the present invention produced in Examples 2, 3, 5, and 6 above, and the laminate produced using the gas barrier vapor-deposited laminate produced in Comparative Examples 3 and 4 were used. The bag is then used to produce a packaging bag that is heat-sealed on three sides. After that, the contents are filled from the opening of the packaging bag, and then the opening is heated. -Tossed to produce a package.
Next, the package manufactured above was retorted at 120 ° C. for 30 minutes.
The oxygen permeability was measured for the packaging bag before and after the retort treatment.
(1). Measurement of oxygen permeability
Measurement was performed using a measuring instrument (model name, OXTRAN 2/20) manufactured by MOCON, USA under the conditions of a temperature of 25 ° C. and a humidity of 90% RH.
The results measured above are shown in Table 2 below.
[0037]
[Table 2]
[0038]
As is clear from the results shown in Table 2 above, the packaging bag made using the laminate using the gas barrier vapor-deposited laminate according to the present invention has excellent oxygen permeability and is used as a gas barrier material. It turned out to be useful.
[0039]
【The invention's effect】
As is apparent from the above description, the present invention improves the heat resistance of the plastic substrate itself by providing a primer coat layer of an organic compound on the surface of the plastic substrate as the substrate. Focusing on the fact that the surface smoothness is improved by covering the unevenness of the surface, the surface wettability, the affinity, etc. are improved, and the tight adhesion to the deposited thin film layer of metal or metal oxide can be enhanced. First, a primer coat layer made of an organic compound is provided on at least one surface of a plastic substrate, and then a vapor deposition thin film layer of metal or metal oxide is provided on the surface of the primer coat layer made of the organic compound. Furthermore, an organic compound vapor deposition thin film layer is sequentially provided on the surface of the metal or metal oxide vapor deposition thin film layer to produce a vapor deposition laminate, and a plastic substrate and a metal or metal oxide vapor deposition thin film layer, Organic Adhering tightly through a primer coat layer with a compound, there is no phenomenon such as delamination between the layers, and it is excellent in oxygen permeability, water vapor permeability, etc., and extremely useful barrier deposition A laminate can be produced.
[Brief description of the drawings]
FIG. 1 is a schematic cross-sectional view showing a layer configuration of an example of a gas barrier vapor deposition laminate according to the present invention.
FIG. 2 is a schematic configuration diagram showing an example of a configuration of a method for producing a gas barrier vapor deposition laminate according to the present invention.
[Explanation of symbols]
1 Gas barrier vapor deposition laminate
2 Plastic substrate
3 Primer coat layer with organic compounds
4 Metal or metal oxide thin film layer
5 Organic compound thin film layer
11 Winding type vacuum evaporation system
12 Vacuum chamber
13 Unwinding roll
14 Guide roll
14 'guide roll
15 Guide Roll
15 'guide roll
16 coating drum
17 crucible
18 Metal or metal oxide
19 Mask
20 crucible
21 Organic compounds
22 Winding roll

Claims (1)

  1. Coating on which at least one surface of the plastic substrate is made of nitrified cotton and polyurethane resin or saturated polyester resin as the main components of a vehicle, and a curing agent made of an isocyanate compound is added thereto. A primer coat layer made of the composition , an aluminum vapor deposition film, a metal or metal oxide vapor deposition thin film layer comprising an aluminum oxide vapor deposition thin film or a silicon oxide vapor deposition thin film, and an organic compound vapor deposition thin film layer comprising a synthetic wax are sequentially formed. A gas barrier vapor-deposited laminate provided in the above.
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JP2008235292A (en) 2005-07-07 2008-10-02 Sharp Corp Composite substrate and manufacturing method thereof
WO2007111074A1 (en) 2006-03-24 2007-10-04 Konica Minolta Medical & Graphic, Inc. Transparent barrier sheet and method for producing transparent barrier sheet
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US8033882B2 (en) 2007-09-19 2011-10-11 Fujifilm Corporation Light-emitting device or display device, and method for producing them
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