JP5386309B2 - LAMINATE MANUFACTURING METHOD, LAMINATE, AND PACKAGING CONTAINER USING THE SAME - Google Patents

Description

The present invention relates to a method for producing a laminate using a surface-modified film, a laminate, and a packaging container using the laminate. Furthermore, in detail, by not using an adhesive and an anchor coating agent, generation of VOC (volatile organic compound) is completely eliminated, and a laminate manufacturing method and laminate excellent in environmental measures and energy saving measures, and The present invention relates to a clean packaging container that does not generate low-molecular components due to an adhesive and an anchor coat agent, which can be a source of contamination to contents produced using the above-mentioned.
Moreover, the laminated body by this invention is used for various uses, such as a decorative sheet, an optical film, a protective film, and a packaging container. In addition, the packaging container prepared using the laminate according to the present invention includes liquid seasonings, liquid detergents, liquid bleaches, liquid waxes, hair care products (including shampoos, rinses, conditioners, etc.), chemicals, liquids Widely used in packaging containers for various liquid products such as cosmetics, packaging containers for refilling, and various packaging containers for food, electronic parts, medical parts, medical equipment parts, precision machine parts and the like.

Traditionally, seasonings such as salt and pepper and powdered powder such as coffee powder are stored and stored in plastic packaging containers for refilling, and they are transferred to hand-held desktop containers when used. Things have been done.
In recent years, liquid seasonings such as cooking sauce, liquid detergents for dishes and clothing, liquid bleach, liquid wax, hair care products (including shampoos, rinses, conditioners, etc.), liquid cosmetics, etc. In order to sell various liquid products, refill packaging containers have been used.
For example, instead of conventional cans, bottles, or plastic bottles equipped with hand pumps, they are stored in refillable plastic packaging containers made of multilayer film and sold to general consumers. Consumers who purchase the product can refill the contents with their own plastic bottles.
As a social background for this phenomenon, companies that manufacture and sell these products can reduce the weight and cost of the packaging containers by reducing the weight of the synthetic resin used in the product packaging containers. In addition to pursuing economic efficiency, such as reducing the volume of packaging containers that become waste after the contents have been used up, in order to make it easier to dispose of them, not only resource saving and the global environment This is because there is an increasing demand for sufficient consideration for protection measures.

Electronic parts such as semiconductors and liquid crystal monitors, medical parts, medical equipment parts, precision machine parts, etc. are transported on trays made of plastic or housed in boxes. These parts are required to have high cleanliness and must be protected from dirt, dust, microorganisms, chemicals, etc. during transportation, moisture, extreme temperature changes, ultraviolet rays, and the like. Therefore, the tray and the entire storage box are transported in a state of being covered with the packaging container.
Examples of packaging containers used for packaging electronic components include plastic bags and sheet-molded containers. Electronic parts and the like are housed in these packaging containers, and are shipped in a sealed state with the opening of the packaging container sealed.

In such a packaging container, as a constituent material of the packaging container, a combination of two or more kinds of films, an aluminum foil, a vapor deposition film (a laminated thin film of aluminum, silica, alumina, etc. on a base material), etc. Used. As the laminate, for example, after filling the contents, when the filling port of the packaging container is sealed by welding with a heating bar, so-called heat sealing, the inner surface of the laminate that becomes the heat seal surface has excellent heat sealability. A polyolefin resin layer such as polyethylene is used as the heat seal layer.
The laminate is laminated with polyamide, polyester, aluminum foil, a vapor deposition film, etc. in order to reinforce the strength or impart other functions. For this reason, preparing the laminated body which laminated | stacked the polyethylene resin excellent in heat-sealability in advance, for example, a polyamide resin film, and shape | molding in the final packaging container is performed.

It also has various functions depending on how the packaging container is used, such as providing light-shielding properties, providing a resealing chuck, and providing a self-supporting shape. It is necessary to make it a wrapping container.
Moreover, a packaging container can be suitably selected from the shape of a well-known packaging container according to the form and property of the content to fill. For example, a standing pouch shape (for example, Patent Documents 1 and 2), a three- or four-side sealed flat bag shape (for example, Patent Document 3), a gusset bag body, a pillow packaging shape, a storage case, and the like are preferably used.
In addition, for applications such as electronic parts, medical parts, medical equipment parts, precision machine parts, etc., packaging is performed using a base film whose cleanliness is maintained in a specially cleanliness-controlled work environment. After the laminated body for the material is produced, a clean packaging body using the laminated body (hereinafter, the packaging bag and the packaging container are collectively referred to as a packaging body) is produced.

Conventionally, as a method of laminating a film used for a laminate, a dry laminating method in which an adhesive is used to bond two or more kinds of films together, or an anchor coating agent is used. The laminated body which laminated | stacked the film by the film sand system to perform, the extrusion laminating system, etc. was produced.
Adhesive strength may be insufficient unless an adhesive or anchor coating agent is used. However, when using an adhesive or an anchor coating agent, it is an environmental problem that VOCs (volatile organic compounds) generated by evaporating and drying the solvent in the laminating process of these films are dissipated into the atmosphere. Yes. For this reason, as a more preferable method for producing a laminate for a packaging container, there is a demand for a method capable of producing a laminate having a required adhesive strength without using an adhesive or an anchor coat agent.

In response to such a demand, various proposals have been made regarding a method for producing a laminate without using an adhesive or an anchor coat agent by performing a treatment for increasing the adhesive strength (for example, Patent Documents 4 to 4). 10).
In Patent Document 4, at least one surface of a plastic substrate is oxidized by corona treatment, plasma treatment, flame plasma treatment, electron beam irradiation, ultraviolet irradiation, etc., and at least one surface of a melt-extruded film is subjected to ozone treatment. An extrusion laminating method in which both are brought into contact with each other and pressure-bonded is described.
In Patent Document 5, at least one surface of a plastic substrate is subjected to electron beam irradiation treatment, low pressure plasma treatment, atmospheric pressure plasma treatment, or corona discharge treatment in an atmosphere of an inert gas such as argon, helium, krypton, neon, xenon, and nitrogen. And an extrusion laminating method in which at least one surface of a melt-extruded film is subjected to ozone treatment and then brought into contact with each other and pressure-bonded.

In Patent Document 6, in order to activate the surface of the synthetic resin and improve the adhesion to the printing ink and the metal vapor deposition film, a mixed gas atmosphere substantially composed of nitrogen and carbon dioxide (preferably an oxygen concentration of 0.1 vol. % Or less), a surface treatment method for a synthetic resin is described.
Patent Document 7 discloses the number of nitrogen and carbon atoms on the surface of a base film by ESCA method by corona discharge treatment in nitrogen gas (oxygen concentration of 3 vol% or less), carbon dioxide gas or nitrogen / carbon dioxide mixed gas atmosphere. A surface to be processed having a ratio (N / C) in the range of 0.001 to 0.1 is generated, and a water / lower alcohol mixed solution or water is used as a solvent on the surface to be processed. A method for producing a gas barrier film is described in which a coating agent containing a layered compound as a main constituent is applied and dried to form a coating film.

Patent Document 8 discloses a method of laminating at least two layers of polyolefin resins such as unstretched polyethylene (PE) and unstretched polypropylene (CPP) without using an adhesive. Specifically, the surface of the laminated resin is subjected to low-temperature plasma treatment using a scanning glow discharge plasma apparatus, and then laminated by thermocompression bonding.
Patent Document 9 discloses that substrates obtained by plasma-treating the surface of a fluororesin sheet with an atmospheric pressure plasma treatment apparatus do not use an adhesive and do not change the structure / composition, and the melting point of the substrate or less. A bonding apparatus and a bonding method for bonding by pressure bonding at a temperature are shown.
In Patent Document 10, an aramid paper composed of plasma-treated aramid fibers and aramid pulp and a plasma-treated polyester film are continuously laminated and bonded using a pressure roll at a temperature of room temperature to 200 ° C. An adhesive-free aramid-polyester laminate is shown.

JP 2001-058655 A Japanese Patent Laid-Open No. 08-324590 Japanese Patent Laid-Open No. 11-059704 JP 7-314629 A JP-A-9-234845 Japanese Patent Publication No.57-30854 Japanese Patent Laid-Open No. 9-1111017 JP-A-3-162420 JP 2008-075030 A JP 2008-183868 A

  However, in the methods proposed in Patent Documents 4 and 5, the bonding strength may be insufficient only by performing a combination of a corona treatment in a known air atmosphere and a UV / ozone treatment.

  Patent Documents 6 and 7 describe a method for improving adhesion by modifying the surface of a synthetic resin by corona discharge treatment in an atmosphere containing nitrogen and substantially no oxygen. However, these patent documents only describe the adhesion to a coating film containing printing ink, a metal vapor-deposited film, a water-soluble polymer and an inorganic layered compound as main components. In order to confirm the adhesiveness between the surface treatment surface of the synthetic resin activated by such a surface treatment method and the resin film by thermocompression bonding, the present inventor has performed a corona discharge treatment in a nitrogen gas atmosphere. On the other hand, when an attempt was made to produce a laminate by thermally laminating a resin film having an untreated surface, sufficient adhesive strength could not be obtained.

In Patent Document 8, a non-polar thermoplastic resin, for example, a surface of a polyolefin resin such as unstretched polyethylene (PE) is subjected to low-temperature plasma treatment using a scanning glow discharge plasma apparatus, and then subjected to thermocompression bonding. Lamination is disclosed. In addition, when laminating a polar thermoplastic resin such as polyester and a nonpolar thermoplastic resin, it is processed only with the nonpolar thermoplastic resin by the modulated magnetic field plasma apparatus, but the polar thermoplastic resin. The surface is preferably used without plasma treatment because a high interlayer adhesion strength can be obtained. In this case, since it was confirmed by ESCA analysis that a C—O group and a C═O group were generated by the treatment with the modulated magnetic field plasma apparatus, these generated functional groups contribute to adhesion.
However, according to the embodiment, for example, the thermocompression bonding temperature when PP and LDPE are thermocompression bonded is set to 100 ° C., but no pressure is shown, so that industrial utilization cannot be achieved.

Patent Document 9 uses an atmospheric pressure plasma processing apparatus in which a lower alcohol which is a primary alcohol or a secondary alcohol having 4 or less carbon atoms is vaporized and mixed with an inert gas and supplied to an electrode. A method is disclosed in which surface modification is performed on substrates whose surfaces are made of a fluororesin, and the surface-modified substrates are thermocompression bonded at a temperature equal to or lower than the melting point of the substrates.
Although it is said that hydrophilicity is imparted to the fluororesin on the surface by the surface modification, there is not shown what defines a standard for judging a preferable treatment state of the plasma-treated resin surface. In addition, the thermocompression bonding temperature at the time of thermocompression bonding is, for example, 200 ° C. or less for polytetrafluoroethylene (PTFE) having a melting point of 327 ° C., but no pressure is shown. I can't.

Patent Document 10 discloses that an aramid paper composed of plasma-treated aramid fibers and aramid pulp and plasma-treated polyethylene terephthalate or polyethylene naphthalate at a temperature of room temperature to 200 ° C. under a pressure of 200 kgf / cm or more. A method of continuously laminating using a pressure roll is disclosed.
By surface modification, certain functional groups such as COOH groups and OH groups can be formed on the film surface and can be firmly laminated and bonded at low temperatures. No definition of the criteria to do is shown. In addition, since the plasma treatment is a well-known method for enhancing the adhesiveness of various resins, a detailed explanation of the plasma treatment is omitted, and a specific explanation of the plasma treatment is not described. Therefore, industrial use cannot be achieved.

  Further, the dry lamination method using an adhesive, the film sand method using an anchor coating agent, and the extrusion lamination method have problems in terms of environmental measures and energy saving measures because organic solvents are used. Furthermore, since there is a risk of migration of residual solvent and low molecular components, there is a problem that the influence of contamination on the contents is unavoidable. For these reasons, it is required to reduce the amount of the adhesive and the anchor coating agent as much as possible when manufacturing a laminate in which films are laminated.

In the prior art, in heat lamination using the same type of film, for example, in OPP / CPP, etc., it was performed without using an adhesive and an anchor coat agent. In the case of bonding without using an anchor coating agent, the adhesive strength was weak and it was not practically used.
Thus, in the prior art, by sticking different types of films together without using an adhesive and an anchor coat agent, the generation of VOC (volatile organic compound) is completely eliminated, and it is used for environmental measures and energy saving measures. An excellent laminate and a packaging container produced using the same have not been known.

  The present invention has been made in view of the above. That is, the object of the present invention is to eliminate the generation of VOC (volatile organic compound) by not using an adhesive and an anchor coating agent, and to provide a laminate manufacturing method and laminate excellent in environmental measures and energy saving measures, It is an object of the present invention to provide a clean packaging container free from the generation of low-molecular components derived from an adhesive and an anchor coat agent, which can be a source of contamination of contents using the laminate.

In the present invention, in order to solve the above-mentioned problem, a method for producing a laminate in which a first base material and a second base material made of different types of thermoplastic resin films or cellophane films are bonded, The surface of the first substrate that has been subjected to surface modification using the atmospheric pressure plasma processing apparatus, the surface on which the heat-adhesive modified layer is formed by the surface modification of the first substrate, and the second substrate are large. Surface modification is performed using an atmospheric pressure plasma treatment apparatus, and the surface on which the thermal adhesion modified layer is formed by the surface modification of the substrate or the air corona treated surface of the substrate subjected to the air corona treatment is opposed to the surface. Then, an adhesive and an anchor coating agent are applied using a film sand method in which a molten resin film is extruded between the different films and laminated while performing ozone treatment on the surface of the molten resin film to be joined with the first substrate. Without continuous paste It provides a method for producing a laminate, characterized by.
Further, if the second base material is not used, it can be used as a laminate of an extrusion laminate method.

  That is, this invention is a method of manufacturing the laminated body which bonded the 1st base material which consists of a different kind of thermoplastic resin film or a cellophane film, and a 2nd base material, Comprising: Thickness is 10-500 micrometers. Yes, the first base material fed out from the roll body wound with the first base material and the second base material, each of which is a long film having a length of 3 to 10,000 m, The second substrate has a surface on which a heat-adhesive modified layer is formed by surface modification by an atmospheric pressure plasma processing apparatus, and the second substrate has a heat-adhesive modified layer formed by surface modification by an atmospheric pressure plasma processing apparatus. A surface having an air corona treatment using an air corona treatment apparatus, a surface on which a heat adhesion modified layer of the first substrate is formed, and a heat adhesion modified layer of the second substrate The surface on which the surface is formed or the surface treated with air corona The molten resin film is extruded between the first base material and the second base material without applying an adhesive and an anchor coating agent, and is combined with the first base material of the molten resin film. Provided is a method for producing a laminate, which is characterized by continuously laminating with a cooling nip roll while performing ozone treatment on the surface.

The present invention is also a method for producing a laminate in which a first base material made of different types of thermoplastic resin films or cellophane films and a molten resin film are laminated, wherein the first base material and the molten resin are provided. When laminating the film, the first base material on which the heat adhesion modified layer is formed by surface modification of the film using an atmospheric pressure plasma processing apparatus in advance is different from the first base material. A surface of the first base material on which the thermoadhesive modified layer is formed using a third base material which is a type of thermoplastic resin film and subjected to air corona treatment; After the air corona-treated surfaces are opposed to each other and thermocompression bonded without applying an adhesive and an anchor coating agent, a test laminate is obtained, and then the adhesive force on the bonding surface of the test laminate is measured, and the first The state of formation of the thermal adhesion modified layer of the base material Verify whether, a thickness of 10 to 500 [mu] m, a length fed from wound roll body of said first substrate comprising a long film of 3～10,000M, the first group The material has a surface on which a thermal adhesion modified layer is formed by surface modification by an atmospheric pressure plasma processing apparatus, and on the surface on which the thermal adhesion modified layer of the first substrate is formed, Without applying the adhesive and the anchor coating agent, extruding the molten resin film and continuously bonding with a cooling nip roll while performing ozone treatment on the surface of the molten resin film to be combined with the first substrate. Provided is a method for producing a laminate.

  In the manufacturing method of the laminated body of this invention, when bonding a said 1st base material and a said 2nd base material, or when laminating | stacking a said 1st base material and a molten resin film, it is beforehand Further, the first base material on which the thermal adhesion modified layer is formed by surface modification of the film using an atmospheric pressure plasma processing apparatus, and a thermoplastic resin film of a different type from the first base material. And using the third base material that has been subjected to air corona treatment, the surface of the first base material on which the heat-adhesive modified layer is formed and the air corona treatment surface of the third base material are opposed to each other, After applying a thermocompression bonding without applying an adhesive and an anchor coating agent to obtain a test laminate, the adhesive strength on the bonding surface of the test laminate is measured, and the thermal adhesion of the first substrate is improved. It is preferable that the quality of the quality layer is confirmed.

When the first substrate is a polyamide (PA) resin film, an unstretched polyethylene (PE) resin film treated with air corona is used as the third substrate, and the temperature is 160 ° C. and the applied pressure is 0.4 MPa. The adhesive strength when heated and pressure-bonded for 10 seconds is JIS K 6854-1, “Adhesive Peeling Adhesive Strength Test Method Part 1: 90 degree peeling” and the value measured by the measuring method is 9 Confirm that it is 8N / 25.4mm or more,
When the first substrate is a polyethylene terephthalate (PET) resin film, an unstretched polyethylene (PE) resin film that has been subjected to air corona treatment is used as the third substrate, and the temperature is 160 ° C. and the applied pressure is 0. The adhesive force when held at 4 MPa for 10 seconds and thermocompression bonded is the value measured by the measurement method specified in JIS K 6854-1 “Adhesive Peeling Adhesive Strength Test Method Part 1: 90 degree peeling” 5.9N / 25.4mm or more is confirmed,
When the first substrate is a cellophane film, an air-corona-treated unstretched polyethylene (PE) resin film is used as the third substrate and held at a temperature of 160 ° C. and a pressure of 0.4 MPa for 10 seconds. The adhesive strength when thermocompression bonding was performed was 2.0 N / 25 as measured by the measurement method defined in JIS K 6854-1, “Adhesive Peeling Adhesive Strength Test Method Part 1: 90 ° Peeling”. It is preferable to confirm that the thickness is 4 mm or more.

It is preferable to include an aging process in which the laminate is allowed to stand at room temperature for 10 days to 1 month or at 40 to 60 ° C. for 1 to 3 days after the bonding process.
The first substrate is made of a film group consisting of polyethylene terephthalate (PET), polyamide (PA), polyethylene naphthalate (PEN), polyacrylonitrile (PAN), polycarbonate (PC), polyimide (PI), and cellophane. Preferably, the second substrate is an unstretched polyethylene (PE) or a coextruded film of unstretched polyethylene and unstretched polypropylene (PE / CPP).
Further, the first substrate is a film group consisting of polyethylene terephthalate (PET), polyamide (PA), polyethylene naphthalate (PEN), polyacrylonitrile (PAN), polycarbonate (PC), polyimide (PI), cellophane. Preferably, the molten resin is one selected from the group consisting of polyethylene (PE).
It is preferable that a printed layer is formed on at least one surface of the film serving as the first substrate.

Moreover, this invention provides the laminated body manufactured by said manufacturing method of the laminated body.
Further, the present invention uses a laminate described above, the second substrate or the molten resin film to provide a packaging container which is characterized by comprising manufactured such that the inner surface side as a sealant layer.

  Moreover, this invention is the laminated body which bonded the 1st base material and 2nd base material which consist of a different kind of thermoplastic resin film or a cellophane film, Comprising: The said 1st base material is polyethylene. It is one kind selected from a film group consisting of terephthalate (PET), polyamide (PA), polyethylene naphthalate (PEN), polyacrylonitrile (PAN), polycarbonate (PC), polyimide (PI), cellophane, The second substrate is unstretched polyethylene (PE), or a co-extruded film of unstretched polyethylene and unstretched polypropylene (PE / CPP), and the first substrate and the second substrate have a thickness. It consists of a long film having a length of 10 to 500 μm and a length of 3 to 10,000 m. In the bonding surface of the laminate, the first The material has a surface on which a heat-adhesive modified layer is formed by surface modification using an atmospheric pressure plasma processing apparatus, and the second base material has a heat-adhesive modified layer formed by surface modification using an atmospheric pressure plasma processing apparatus. A surface having a formed surface or a surface that has been subjected to air corona treatment using an air corona treatment apparatus, the surface on which the thermal adhesion modifying layer of the first substrate is formed, and the thermal adhesion modification of the second substrate. The surface of the molten resin film that is combined with the first base material is subjected to ozone treatment through the molten resin film while the surface on which the porous layer is formed or the surface that has been subjected to the air corona treatment is opposed, and the adhesive and Provided is a laminate characterized by being bonded without using an anchor agent.

Further, the present invention is different types of a thermoplastic resin film or laminate in which the first substrate comprising a cellophane film and a molten resin film is laminated, and a molten resin film and the first base member When laminating, the first base material on which the heat-adhesive modified layer is formed by surface modification of the film using an atmospheric pressure plasma processing apparatus in advance, and a different kind of heat from the first base material Using a third base material that is a plastic resin film that has been subjected to air corona treatment, a surface on which the heat-adhesive modified layer of the first base material is formed, and an air corona treatment surface of the third base material The test laminate is obtained by thermocompression bonding without applying an adhesive and an anchor coating agent, and the first substrate is measured by measuring the adhesive force on the bonding surface of the test laminate. The quality of the heat-adhesive modified layer was confirmed. It has been, the first substrate is a polyethylene terephthalate (PET), polyamide (PA), polyethylene naphthalate (PEN), polyacrylonitrile (PAN), polycarbonate (PC), polyimide (PI), a film group consisting of cellophane The melted resin is polyethylene (PE), the first base material has a thickness of 10 to 500 μm, and a length of 3 to 10,000 m. And the first substrate has a surface on which a heat-adhesive modified layer is formed by surface modification using an atmospheric pressure plasma processing apparatus on the bonding surface of the laminate. The surface of the molten resin film that is to be combined with the first base material is subjected to ozone treatment without using an adhesive and an anchor agent on the surface on which the heat-adhesive modified layer is formed. And a laminated body characterized by being laminated.

  Moreover, this invention provides the packaging container characterized by being manufactured using said laminated body so that a said 2nd base material or a molten resin film may become an inner surface side as a sealant layer.

According to the present invention, since no adhesive and anchor coating agent are used, it is not necessary to take environmental measures for VOC (volatile organic compound) generated by evaporating and drying the solvent.
Further, in the method for producing a laminate of the present invention, since no adhesive or anchor coating agent is used, an organic solvent is not used, so a drying furnace for drying and removing the solvent is not required, and environmental measures and energy saving measures are taken. This can reduce the environmental load.

According to the invention which concerns on Claim 1, it is a method of manufacturing the laminated body which bonded the 1st base material which consists of a different kind of thermoplastic resin film or a cellophane film, and a 2nd base material, Comprising: Adhesive And the manufacturing method which obtains the laminated body in which the anchor coating agent is not used can be provided.
For this reason, compared with the method of manufacturing a laminate by dry lamination using an adhesive, the method of manufacturing a laminate according to the present invention does not use an organic solvent. From the viewpoint of environmental measures and energy saving measures without requiring an exhaust gas treatment device, the environmental load can be reduced, which is very good.

According to the second aspect of the present invention, there is provided a method for producing a laminate in which a first substrate made of different types of thermoplastic resin films or cellophane films and a molten resin film are laminated, and an adhesive and an anchor coat The manufacturing method which obtains the laminated body in which the agent is not used can be provided.
For this reason, compared with the method of manufacturing a laminate by dry lamination using an adhesive, the method of manufacturing a laminate according to the present invention does not use an organic solvent. From the viewpoint of environmental measures and energy saving measures without requiring an exhaust gas treatment device, the environmental load can be reduced, which is very good.

  Further, according to the inventions according to claims 3 and 4, the surface of the film used for the laminate is provided with a heat-adhesive modified layer having a necessary adhesive force by surface modification using an atmospheric pressure plasma processing apparatus. A laminate that is formed of quality and can be used in a practical packaging container can be obtained.

  Moreover, according to the invention concerning Claims 5-9, the laminated body excellent in the environmental measure and the energy-saving measure which does not use the adhesive agent and the anchor coat agent can be obtained.

In addition, according to the inventions according to claims 10 and 11 , an adhesive that does not use an adhesive and an anchor coat agent, and that can be a source of contamination to contents using a laminate excellent in environmental measures and energy saving measures. In addition, a clean packaging container free from the generation of low molecular components derived from the anchor coat agent can be obtained.

The invention according to claim 12 is a laminate in which a first base material and a second base material made of different types of thermoplastic resin films or cellophane films are bonded to each other, and includes an adhesive and an anchor. A laminate in which no coating agent is used can be provided.
For this reason, the laminate of the present invention does not use an organic solvent as compared with a laminate produced by an extrusion laminating method using a film sand method that uses an anchor coating agent, so that the solvent is removed by drying. From the viewpoint of environmental measures and energy saving measures without requiring a drying furnace and an exhaust gas treatment device, the environmental load can be reduced.

The invention according to claim 13 is a laminate in which a first substrate made of different types of thermoplastic resin films or cellophane films and a molten resin film are laminated, wherein the adhesive and the anchor coating agent are An unused laminate can be provided.
For this reason, the laminate of the present invention does not use an organic solvent as compared with a laminate produced by an extrusion laminating method using a film sand method that uses an anchor coating agent, so that the solvent is removed by drying. From the viewpoint of environmental measures and energy saving measures without requiring a drying furnace and an exhaust gas treatment device, the environmental load can be reduced.

In addition, according to the inventions according to claims 14 and 15 , the occurrence of low molecular components caused by the adhesive and the anchor coating agent, which can be a source of contamination to the contents, using a laminate excellent in environmental measures and energy saving measures. It is possible to obtain a clean packaging container that does not have any.

It is a conceptual diagram which shows an example of the manufacturing method of the laminated body concerning this invention. It is a conceptual diagram which shows the other example of the manufacturing method of the laminated body concerning this invention. It is a schematic sectional drawing which shows an example of the laminated body concerning this invention, Comprising: (a) is a schematic sectional drawing before film-sanding, (b) is a schematic sectional drawing after film-sanding. It is a schematic sectional drawing which shows an example of the laminated body concerning this invention, Comprising: (a) is a schematic sectional drawing before carrying out extrusion lamination, (b) is a schematic sectional drawing after carrying out extrusion lamination. It is another example of the laminated body concerning this invention, and is a schematic sectional drawing which shows the laminated body by the film which has a printing layer. (A) is a schematic sectional drawing before film-sanding, (b) is a schematic sectional drawing after film-sanding. It is a schematic sectional drawing which shows an example of the laminated body by a prior art, (a) is a schematic sectional drawing before dry-laminating, (b) is a schematic sectional drawing after dry-laminating.

Hereinafter, the present invention will be described with respect to preferred embodiments.
In the following description, the untreated first base material 1 and the second base material 6 and the surface-treated first base material 5 and the second base material 8 are distinguished by reference numerals, "" Or "surface treated" may be omitted.
As the first base material 5 and the second base material 8 subjected to the surface treatment, the same reference numerals are used without distinguishing between the case where the surface treatment is atmospheric pressure plasma treatment and the case where the surface treatment is air corona treatment.
In addition, as shown in FIG. 1, the untreated first base material 1 and second base material 6 are also objects to be processed (that is, before processing) as shown in FIGS. As shown in FIG. 5, the same reference numerals are used also in the case of representing a portion that has not been processed after the processing.

FIG. 1 is a conceptual diagram showing an example of a method for producing a laminate according to the present invention, in which a first base material and a second base material made of different types of films are bonded together to form a film sand system. Shows a method of manufacturing a laminate.
The first base material 1 and the second base material 6 are each made of a long film, and a roll body 21 around which the first base material 1 is wound and a roll body around which the second base material 6 is wound. 22 is fed out respectively. The first base material 1 becomes the first base material 5 on which the heat adhesion modified layer is formed by surface modification using the atmospheric pressure plasma processing apparatus 23, and the second base material 6 is an air corona. The second substrate 8 is subjected to the air corona treatment by the treatment device (or may be an atmospheric pressure plasma treatment device) 24.
Although FIG. 1 shows a case where surface modification is performed online using the atmospheric pressure plasma processing apparatus 23 and the air corona treatment apparatus 24, the surface modification by the atmospheric pressure plasma processing apparatus is performed in advance. You may use the roll body around which the 1st base material in which the heat adhesive property modification layer was formed, and the 2nd base material by which the air corona treatment was wound were wound.
The surface of the first base material 5 on which the heat adhesion modified layer is formed and the air corona treatment surface of the second base material 8 are opposed to each other, and a molten resin film is applied without applying an adhesive and an anchor coat agent. 27 is extruded between the first base material and the second base material (while performing ozone treatment on the surface of the molten resin film to be combined with the first base material), and then bonded by the cooling nip roll 25 (film sand) ) To obtain the laminate 10. The obtained laminated body 10 may be wound around the roll body 28, or may be cut into a predetermined size to form a sheet-like laminated body (not shown).

FIG. 3 is a schematic cross-sectional view showing an example of a laminate according to the present invention, where (a) is a schematic cross-sectional view before film sanding, and (b) is a schematic cross-sectional view after film sanding. .
In this case, at least one surface of the first base material 1 is subjected to surface modification by an atmospheric pressure plasma processing apparatus to form a heat adhesion modified layer 2. Further, a surface modification layer 7 by air corona treatment or a heat adhesion modification layer 7 by surface modification of the substrate using an atmospheric pressure plasma processing apparatus is formed on one surface of the second substrate 6. The surface of the first base material 5 on which the heat-adhesive modified layer 2 is formed and the surface of the second base material 8 on which the surface modified layer 7 or the heat-adhesive modified layer 7 is formed. The molten resin film 27 (while performing ozone treatment on the surface of the molten resin film to be combined with the first base material) is applied to the first base material and the second base material without applying an adhesive and an anchor coating agent. After being extruded between the substrates, the laminate 10 is obtained by bonding (film sand) with a cooling nip roll (not shown).
This laminated body 10 is a laminated body in which a first base material and a second base material are laminated, in which an adhesive and an anchor coat agent are not used. The molten resin film 27 between the first base material 5 and the second base material 8 becomes a solidified thermoplastic resin layer after cooling.
Since one resin film of the laminate 10 is a thermoplastic resin film having heat sealing properties, the laminate 10 is cut into a predetermined shape and size, and the resin of the heat seal layer is disposed on the inner surface. By heat-sealing as a side, a packaging container can be produced.

FIG. 2 is a conceptual diagram showing another example of a method for producing a laminate according to the present invention, in which a first substrate made of different types of films and a molten resin film are bonded together, and an extrusion laminating method is used. Shows a method of manufacturing a laminate.
The 1st base material 1 consists of a long film, and is drawn | fed out from the roll body 21 around which the 1st base material 1 was wound. The first base material 1 becomes the first base material 5 on which the thermal adhesion modified layer is formed by surface modification using the atmospheric pressure plasma processing apparatus 23.
FIG. 2 shows a case where the surface modification is performed online using the atmospheric pressure plasma processing apparatus 23, but the thermal adhesion modified layer is previously formed by surface modification by the atmospheric pressure plasma processing apparatus. You may use the roll body around which the formed 1st base material was wound.
Without applying the adhesive and the anchor coating agent on the surface of the first base material 5 on which the thermal adhesive property reforming layer is formed, the molten resin film 27 (the surface to be joined with the first base material of the molten resin film). The laminate 11 is obtained by extruding to the surface of the first base material on which the heat-adhesive modified layer 2 is formed, and then laminating with the cooling nip roll 25. The obtained laminate 11 may be wound around a roll body 28, or may be cut into a predetermined size to form a sheet-like laminate (not shown).

FIG. 4 is a schematic cross-sectional view showing an example of a laminate according to the present invention, where (a) is a schematic cross-sectional view before extrusion lamination, and (b) is a schematic cross-sectional view after extrusion lamination. .
In this case, at least one surface of the first base material 1 is subjected to surface modification by an atmospheric pressure plasma processing apparatus to form a heat adhesion modified layer 2. Without applying an adhesive and an anchor coating agent on the surface of the first base material 5 on which the heat adhesion modified layer 2 is formed, the molten resin film 27 (to be combined with the first base material of the molten resin film). The surface of the laminate 11 is subjected to the ozone treatment on the surface) and extruded onto the surface of the first base material on which the heat-adhesive modified layer 2 is formed, and then laminated with a cooling nip roll (not shown). can get.
The laminate 11 is a laminate in which a first base material and a molten resin film are laminated, in which an adhesive and an anchor coat agent are not used. The molten resin film 27 becomes a solidified thermoplastic resin layer after cooling.
Since one molten resin film 27 of the laminated body 11 is made of a thermoplastic resin having heat sealability, the laminated body 11 is cut into a predetermined shape and size, and the resin of the heat seal layer is used. A packaging container can be produced by heat-sealing as the inner surface side.

FIG. 5 is a schematic sectional view showing another example of the laminate according to the present invention, which is a laminate of a film having a printing layer. (A) is a schematic sectional drawing before film-sanding, (b) is a schematic sectional drawing after film-sanding.
In FIG. 5, a printing layer 3 is formed on one side of a first base material 1 made of a film. A surface modification treatment is performed on the printing layer 3 of the first base material 1 on which the printing layer 3 is formed using an atmospheric pressure plasma processing apparatus, and printing of the printing layer 3 and the first base material 1 is performed. A heat adhesion modified layer 2 is formed in a portion where no layer is formed. The surface of the first base material 5 on which the heat-adhesive modified layer 2 is formed and the surface of the second base material 8 on which the surface modified layer 7 or the heat-adhesive modified layer 7 is formed. The laminate 20 is obtained by bonding (film sand) with a cooling nip roll (not shown) without applying an adhesive and an anchor coating agent.
The laminate 20 is a laminate on which a print layer is formed. The laminate 20 has a print layer by cutting the laminate 20 into a predetermined shape and size and heat-sealing the resin of the heat seal layer as the inner surface side. A practical packaging container can be produced.
Note that the first base material having the printed layer can also be used for the extrusion laminating method. For example, as shown in FIGS. 2 and 4, if the second base material is not used, the laminate of the extrusion laminating method is used. Can be used as

FIG. 6 is a schematic cross-sectional view showing an example of a laminate according to the prior art, (a) is a schematic cross-sectional view before dry lamination, and (b) is a schematic cross-sectional view after dry lamination. is there.
A surface modification layer 43 by air corona treatment is formed on one surface of the first base material 41, and an adhesive layer 45 is formed on the surface modification layer 43. The first base material 41 is dry-laminated with the surface of the second base material 42 on which the surface modification layer 44 is formed by the air corona treatment via the adhesive layer 45, and the laminate 40 is obtained.

  Moreover, when obtaining a laminated body by the film sand using the anchor coat agent of a prior art, the surface modification layer by the air corona treatment is formed in the single side | surface of the 1st base material, The surface of the 1st base material The anchor coating agent is applied to the surface of the first base material that faces the surface of the second base material on which the surface base layer is formed by air corona treatment, and the surface of the second base material that is combined with the molten resin film. After applying the film, the molten resin film is extruded between the first base material and the second base material while applying ozone treatment to the surface of the molten resin film that is to be combined with the first base material, and then applied with a cooling nip roll. Combine (film sand) to obtain a laminate.

By the way, the film used for the laminate by the film sand system of the present invention has a thickness of 10 on which at least one surface has a heat-adhesive modified layer formed by surface modification using an atmospheric pressure plasma processing apparatus. A film serving as a first substrate having a thickness of ˜500 μm (referred to as a modified first substrate), a resin film serving as a second substrate treated with an air corona having a thickness of 10 to 500 μm, subjected to an air corona treatment ( A second substrate having a thickness of 10 to 500 μm, on which at least one surface is formed with a heat-adhesive modified layer by surface modification using an atmospheric pressure plasma processing apparatus. It is a resin film (referred to as a modified second substrate) serving as a base material, and there are the following two combinations of films constituting the laminate by the film sand system of the present invention.
(1): (modified first substrate) / (air corona-treated second substrate)
(2): (modified first substrate) / (modified second substrate)

Moreover, when using the laminated body by this invention for a packaging container, the thickness of the film of a 1st base material and a 2nd base material each produces a laminated body using a film about 10-100 micrometers. However, it is preferable for maintaining the flexibility of the laminate and improving the processability of the packaging container in the manufacturing process. In addition, for the consumer who actually holds the packaging container, the thickness of the laminate used in the packaging container is preferably about 30 to 200 μm from the viewpoint of touch.
Such a laminate can be suitably used for a packaging container. For example, a bag can be obtained by folding the laminate into two in order to use unstretched polyethylene (PE) as a heat seal layer, and heat-sealing three sides.
In addition, by stacking two laminated bodies cut to a predetermined size, heat-sealing both side ends, and further heat-sealing the laminated body for the bottom folded in two, thereby making a standing pouch type self-supporting type, A packaging container can be obtained.
In addition, in a refilling packaging container, a self-standing standing pouch is provided, and furthermore, a packaging container that simplifies the refilling operation of contents can be obtained by arranging spouts in various easy-to-pour shapes. Can do.
In addition, for use in applications such as electronic parts, medical parts, medical equipment parts, precision machine parts, etc., a base film with cleanliness maintained is used in the work environment in a cleanroom with special cleanliness control. After the laminate according to the present invention is produced, a clean package using the laminate can be produced.

  Here, the surface on which the heat adhesion modified layer is formed by the surface modification of the film of the first substrate by the atmospheric pressure plasma treatment apparatus is opposed to the air corona treatment surface of the thermoplastic resin film subjected to the air corona treatment. Thus, the adhesive strength when thermocompression bonding is carried out without applying an adhesive and an anchor coating agent is defined in JIS K 6854-1 “Adhesive Peeling Adhesive Strength Test Method Part 1: 90 Degree Peeling” It is necessary that surface modification using an atmospheric pressure plasma processing apparatus is performed so that the value measured by the measurement method is equal to or greater than a predetermined value.

  In the prior art, by surface modification using atmospheric pressure plasma treatment, certain functional groups such as COOH groups and OH groups are formed on the film surface, and can be firmly laminated and bonded at low temperatures. However, there is no description that defines a standard or method for judging a preferable treatment state of the film surface subjected to the atmospheric pressure plasma treatment.

  The present inventors have noticed that the adhesive strength of the films laminated by thermocompression bonding differs depending on the subtle difference in the state of atmospheric pressure plasma treatment. If the surface on which the thermal adhesion modified layer of the film treated with atmospheric pressure plasma is formed and the air corona treated surface of the air-corona-treated thermoplastic resin film face each other and thermocompression-bond, the atmospheric pressure plasma treatment apparatus is It has been found that the quality of the finished surface modification used can be judged, and the present invention has been achieved.

In addition, the surface on which the thermal adhesion modified layer of the film serving as the first base material subjected to the atmospheric pressure plasma treatment is formed and the second base material are subjected to surface modification using an atmospheric pressure plasma processing apparatus. An adhesive and an anchor coating agent are applied so that the surface on which the heat-adhesive modified layer is formed by surface modification of the substrate or the air-corona-treated surface of the air-corona-treated substrate is opposed to the surface. Without extruding the molten resin film between the first base material and the second base material, the surface of the molten resin film bonded to the first base material is bonded with a cooling nip roll while performing ozone treatment. If (film sand) is performed, a laminate that can be used for a packaging container body can be obtained.
For example, as shown in FIGS. 2 and 4, if the second base material is not used, it can be used as a laminate of an extrusion lamination method.

(Resin film)
Resin films that can be used in the present invention include polyethylene terephthalate (PET) resin, polyamide (PA) resin, unstretched polyethylene (PE) resin, co-extruded resin film (PE / CPP), polyethylene naphthalate (PEN) resin, polyacrylonitrile (PAN) resin, polycarbonate (PC) resin, polyimide (PI) resin, and other resin films. The melting points of these thermoplastic resins are polyethylene terephthalate (252 ° C.), polyamide (220 ° C.), unstretched polyethylene (105 to 140 ° C.), co-extruded resin film (PE / CPP) of unstretched polyethylene and unstretched polypropylene, respectively. ) (105 to 165 ° C.), polyethylene naphthalate (about 270 ° C.), polyacrylonitrile (no melting point), polycarbonate (no melting point), polyimide (no melting point). Polyamide resin is a linear polymer whose main chain is composed of repeated amide bonds (—CONH—) formed by the reaction of an acid and an amine. It is what.
Moreover, as a 1st base material, a cellophane film can be used instead of said resin film.

The thickness of the resin film or cellophane film used in the present invention is preferably about 10 to 500 μm. If the thickness is less than 10 μm, it tends to be wrinkled, and it is difficult to perform roll-to-roll processing, resulting in inconvenience in handling. On the other hand, when the thickness exceeds 500 μm, the rigidity is high and the flexibility is lost, and similarly to the case where the thickness is too thin, it is difficult to perform the roll-to-roll processing, resulting in inconvenience in handling. Therefore, when the surface-modified films according to the present invention are bonded to each other by the film sand (or the surface-modified film according to the present invention is laminated with the molten resin film by extrusion lamination) to produce a laminated film, In order to wind up the laminated film as a roll body, it is necessary to consider that the total thickness does not exceed 500 μm.
In addition, when the thickness of the film after being laminated exceeds 500 μm, it is difficult to wind the laminated film around a roll body, so as a laminated film sheet cut at a certain dimensional length. Will be produced. Moreover, when using the laminated body by this invention for a packaging container, the thickness of the film to be used is about 10-100 micrometers, on maintaining the softness | flexibility of a laminated body and improving the workability of a packaging container. Is preferable.

(Print layer)
The film serving as the first base material may have a printed layer formed on at least one side. The position of the printed layer is not particularly limited, such as the surface on the side where the surface treatment of the first substrate is performed, the surface on the side where the surface treatment of the first substrate is not performed, the inside of the first substrate, etc. As shown in FIG. 5, in the case where the printed layer 3 is provided on the surface of the first substrate 5 on which the surface treatment has been performed, the heat adhesion modified layer 2 is also formed on the printed layer 3. obtain.
In order to form the heat adhesion modified layer 2 on the print layer 3, the printing ink constituting the print layer 3 needs to contain a resin component that can be modified by atmospheric pressure plasma treatment. Examples of such a resin component include various ink binder resins such as a urethane resin and an acrylic resin in addition to the thermoplastic resin used for the base film. Furthermore, additives such as various pigments, desiccants and stabilizers are added to the ink.
The printing layer is formed by a known printing method such as an offset printing method, a gravure printing method, or a screen printing method. The thickness of the printing layer is usually about 0.05 to 2.0 μm.
In addition, when the occupation area of the printing layer was sufficiently small compared to the surface area of the first base material, the ozone treatment was performed even if the thermal adhesion reforming layer 2 was not sufficiently formed on the printing layer. It is possible to bond with a molten resin film.

(Laminate manufacturing method)
As a method for producing a laminate by the film sand method using the present invention, the second substrate made of another thermoplastic resin is formed on the surface of the first substrate made of a thermoplastic resin or cellophane film. When bonding a resin film, it can carry out by the process of following (1)-(3).
(1) A surface treatment is performed on the surface of the film of the first base material using an atmospheric pressure plasma processing apparatus to form a heat adhesion modified layer.
(2) The surface of the resin film of the second substrate is subjected to a surface treatment using an atmospheric pressure plasma treatment apparatus to form a heat-adhesive modified layer, or a corona discharge treatment (air corona treatment in an air atmosphere) ) To perform surface treatment.
(3) The surface on which the surface treatment of the second resin film is performed is opposed to the surface of the first base film on which the heat-adhesive modified layer is formed, and an adhesive and an anchor coating agent are added. Extruding the molten resin film between the first substrate and the second substrate while applying ozone treatment to the surface of the molten resin film that is to be combined with the first substrate without coating, and then applying it with a cooling nip roll Combine (film sand).
Further, if the second base material is not used, it can be used as a laminate of an extrusion laminate method.
In the case of the film sand method, the molten resin is preferably a resin suitable for bonding between the first substrate and the second substrate, and in the case of the extrusion laminate method, it is suitable for use as a sealant layer. Resins are preferred. In any case, it is preferable to mainly use polyethylene (PE).
The reactive gas used in the atmospheric pressure plasma processing apparatus is not limited to the one based on nitrogen gas, but may be based on oxygen gas or carbon dioxide gas.

  In the present invention, the two films to be bonded are, for example, a laminated body bonded by a film sand method using polyamide (PA) and unstretched polyethylene (PE) without using an adhesive and an anchor coating agent. Can be obtained. Further, in the present invention, as two films to be bonded, a laminate obtained by bonding with a film sand method using polyethylene terephthalate (PET) and unstretched polyethylene (PE) without using an adhesive and an anchor coat agent. You can get a body.

  The surface modification treatment for the two films used in the laminate of the present invention may be performed first as long as it is a stage before film sanding. Further, the surface modification treatment may be performed simultaneously or in parallel on the two films to be film sanded. When three or more films are to be film-sanded, a laminated film having three or more layers can be produced by repeating the surface modification treatment and the film sanding process on the side to be laminated as many times as necessary. In addition, after both surfaces of the base film are subjected to surface modification treatment, two other films subjected to surface modification treatment are superposed on each surface of the base film, and the film is sanded. It is also possible to produce a three-layer laminated film in which different films are laminated on both sides of the film.

(Corona discharge treatment)
Thermoplastic polyolefin resin films such as polyethylene and polypropylene do not have polar groups in the surface layer, and therefore have low ink printability and adhesion to other resins. For this reason, in order to improve the printability of ink and the adhesion to other resins, the surface of the resin film is modified by corona discharge treatment. The surface modification treatment using corona discharge generates corona discharge in the atmosphere using a high-frequency power supply voltage, irradiates the surface of the resin film with electrons and ions generated along with it, and functional groups are formed on the surface of the resin film. The surface modification of the resin film is performed by adding.

(Corona discharge treatment in air atmosphere (air corona treatment))
In the usual surface modification treatment by corona discharge performed in an air atmosphere, the surface of the resin film subjected to the corona discharge treatment is oxidized, and on the surface of the resin film, a carbonyl group is bonded to the main chain or side chain of the polymer. It is considered that oxygen functional groups such as (> CO) and carboxyl groups (—COOH) are mainly formed.

(Corona discharge treatment in nitrogen gas atmosphere)
By performing corona discharge treatment in a nitrogen gas atmosphere, it is thought that nitrogen functional groups such as amino groups (—NH ₂ ) that are thought to contribute to adhesion are mainly generated in the main chain and side chain of the polymer film surface. It is done. Furthermore, unlike corona discharge treatment (air corona treatment) in a normal air atmosphere, corona discharge treatment in a nitrogen gas atmosphere causes discharge in a nitrogen gas atmosphere, so corona discharge treatment (air corona discharge in an air atmosphere). The generation of a fragile layer due to impurities in the air generated when the treatment is performed is suppressed. Some patent documents describe that nitrogen gas can also be used as an atmospheric gas for atmospheric pressure glow plasma treatment, but it is not atmospheric pressure glow plasma discharge when the discharge state is observed. However, corona discharge in a nitrogen gas atmosphere is capable of lightning-like streamer-like (linear) lightning, that is, a gentler (mild) glow discharge than corona discharge in an air atmosphere by adjusting discharge conditions. Therefore, it can be used for surface modification that is more uniform than air corona treatment.

(Atmospheric pressure glow plasma treatment)
Conventionally, low-temperature plasma treatment for discharging in a vacuum state has been used for surface modification. However, since vacuum equipment is required, there is a drawback that the apparatus becomes large and the operation is complicated. For this reason, an atmospheric pressure plasma treatment apparatus that generates a glow discharge state that can only be generated in a vacuum state at atmospheric pressure and performs surface modification using the reaction radicals, electrons, etc. generated by the glow discharge state is usually It has come to be used simply for improvement and adhesion improvement.

  Atmospheric pressure glow plasma treatment uses a rare gas element such as helium or argon as the atmosphere gas to maintain a stable glow discharge, which is more streamer-like (linear) like lightning, that is, more than corona discharge in an air atmosphere. Uniform surface modification without unevenness is possible. Some patent documents describe that nitrogen gas can also be used as an atmospheric gas for atmospheric pressure glow plasma treatment, but it is not atmospheric pressure glow plasma discharge when the discharge state is observed.

The atmospheric pressure plasma treatment in the present invention is a corona discharge treatment in a nitrogen gas atmosphere or an atmospheric pressure glow plasma treatment in a rare gas atmosphere such as helium or argon.
In atmospheric pressure plasma treatment using oxygen as a reactive gas, oxygen functional groups such as carbonyl groups (> CO) and carboxyl groups (—COOH) are mainly formed on the main chain and side chains of the polymer on the surface of the resin film. . Further, by using nitrogen-based gas as a reaction gas, for example, N ₂ , N ₂ O, NH _3, etc., and further mixing hydrogen (H ₂ ), oxygen (O ₂ ), etc., amino groups, amide groups, etc. The present inventors have confirmed that it can be intentionally introduced.
Further, CH ₄ , CO ₂ or the like may be added to the reaction gas.

In consideration of these, in the present invention, when surface modification treatment is performed on the film surface using atmospheric pressure plasma treatment, corona discharge treatment in a nitrogen gas atmosphere or atmospheric pressure in a rare gas atmosphere such as helium or argon. Performed using glow plasma treatment.
Further, in the present invention, in the atmospheric pressure plasma treatment, the time, the applied power, and the frequency applied to the surface of the film by the atmospheric pressure plasma treatment apparatus are set so that the heat adhesion modified layer is formed on the film surface. Adjust and discharge.

  In atmospheric pressure plasma processing, the processing conditions such as time for applying plasma to the film surface, applied power, frequency, etc., for example, to search for plasma processing conditions for polyamide (PA) resin, PA resin The surface of the film on which the heat-adhesive modified layer is formed is opposed to the air corona-treated surface of an unstretched polyethylene (PE) resin film (Tamapoly Co., Ltd., trade name: SK615P) that has been subjected to air corona treatment. Then, the adhesive strength when heated and pressure-bonded by holding at a temperature of 160 ° C. and a pressure of 0.4 MPa for 10 seconds without applying an adhesive and an anchor coating agent is JIS K 6854-1 “Adhesive peeling adhesion strength” As the strength when peeled at a speed of 5 mm / min by the measurement method specified in “Test method Part 1: 90 degree peel”, As a .8N / 25.4mm or more, the surface modification using atmospheric pressure plasma processing apparatus can be performed by examining the process conditions that have been made.

  In addition, in order to search for the plasma treatment conditions for polyethylene terephthalate (PET) resin, the surface of the PET resin film on which the heat-adhesive modified layer is formed, and the unstretched polyethylene (PE) resin film treated with air corona (Tamapoly Co., Ltd. unstretched polyethylene film, trade name: SK615P) facing the air corona-treated surface and holding for 10 seconds at a temperature of 160 ° C. and a pressure of 0.4 MPa without applying an adhesive and an anchor coating agent. The adhesive strength when thermocompression bonding was performed was peeled off at a speed of 5 mm / min by the measurement method defined in JIS K 6854-1 “Adhesive Peeling Adhesive Strength Test Method Part 1: 90 degree Peeling”. Surface modification using an atmospheric pressure plasma processing apparatus has been performed so that the strength is 5.9 N / 25.4 mm or more. It can be carried out by examining the processing conditions.

  In addition, in order to search for the plasma treatment conditions for the cellophane film, the surface of the cellophane film on which the heat-adhesive modified layer is formed, and an unstretched polyethylene (PE) resin film (manufactured by Tamapoly Co., Ltd.) that has been air corona treated Without facing the air-corona-treated surface of the unstretched polyethylene film, trade name: SK615P), it was thermocompression-bonded by holding at a temperature of 160 ° C. and a pressure of 0.4 MPa for 10 seconds without applying an adhesive and an anchor coating agent. The strength when peeled at a speed of 5 mm / min by the measurement method defined in JIS K 6854-1 “Adhesive Peeling Adhesive Strength Test Method Part 1: 90 ° Peeling”. Investigate the processing conditions under which surface modification is performed using an atmospheric pressure plasma processing apparatus so as to be 0 N / 25.4 mm or more. It can be carried out by.

  Also, when searching for plasma processing conditions for films made of other thermoplastic resins such as polyethylene naphthalate (PEN) resin, polyacrylonitrile (PAN) resin, polycarbonate (PC) resin, polyimide (PI) resin, It can be performed by measuring the adhesive force by a similar method and investigating the processing conditions using an atmospheric pressure plasma processing apparatus.

(Aging process)
The present invention preferably includes an aging step in which the laminate is allowed to stand at room temperature for 10 days to 1 month or at 40 to 60 ° C. for 1 to 3 days after the bonding step. Thereby, the adhesive force can be increased.

  Hereinafter, the present invention will be specifically described with reference to examples.

(Measuring equipment, measuring method)
In order to confirm the effect of the present invention, the experiment conducted was performed using the following measuring equipment and measuring method.
・ Processing conditions by atmospheric pressure plasma treatment Frequency 3 kHz to 13.56 MHz
Irradiation time 0.001 to 10 seconds Distance between electrodes 1 to 4 mm
Since the applied power depends on the scale of the apparatus, the value of the applied power given in the following surface modification examples should be understood as a reference showing relative strength rather than as an absolute numerical value.

-Measurement of adhesion (peeling) strength: Conforms to the measurement method defined in JIS K 6854-1, "Test method for adhesive peel strength, part 1: 90 degree peel".
-Measurement of heat seal strength: Conforms to the measurement method defined in JIS Z 0238 “Test method of heat-sealed soft packaging bag and semi-rigid container 7. Heat seal test of bag”.
-Measurement of tensile strength and tensile elongation: Measured according to the measurement method defined in JIS K 7127 "Plastics-Test method for tensile properties".
-Drop strength: According to JIS Z 0238 "Test method of heat-sealing soft packaging bag and semi-rigid container 9. Drop strength test". The bag was filled with 200 ml of water, the drop height was 1.2 m, and the product temperature and test environment were 5 ° C. The number of drops was 30 times each in the horizontal direction and then in the vertical direction.
・ Measurement of puncture strength: According to JIS Z 1707, “Measurement method for puncture strength of plastic film general rules for food packaging 7.4”.
・ Content resistance suitability test: 200ml filled into a four-sided bag (130mm x 170mm) using contents that degrade the performance of the adhesive and anchor coating agent, and a predetermined number of days have passed (1 month storage at 50 ° C) Later, the adhesive strength of the laminate was evaluated.

(Checking the quality of the heat-adhesive modified layer)
In producing the laminate according to the present invention, first, various films were subjected to surface modification using an atmospheric pressure plasma treatment apparatus, and then a substrate on which the quality of the heat-adhesive modified layer was confirmed was determined. prepare.
Here, the base material A on which the heat adhesive property modified layer is formed and the base material B which is a different type of film from the base material A and subjected to air corona treatment are used to improve the heat adhesive property of the base material A. The surface on which the porous layer is formed and the air corona-treated surface of the base material B are opposed to each other, and a test laminate is obtained by thermocompression bonding without applying an adhesive and an anchor coat agent. The adhesive strength on the bonding surface is measured, and the quality of the heat adhesion modified layer of the substrate A is confirmed.
When the adhesive strength on the bonding surface of the test laminate of the substrate A is a low value, a problem may occur when the laminate of the present invention is produced using the substrate A. For example, when a packaging container is produced using a laminate in which the substrate A is used, it is practical to peel from the bonding surface of the laminate or to be damaged without being able to withstand a drop impact. It becomes difficult to obtain a simple laminate.

Therefore, in order to carry out the method for producing a laminate according to the present invention, the base material A on which the heat-adhesive modified layer by surface modification is formed in advance using the atmospheric pressure plasma processing apparatus to be used. It is necessary to confirm whether or not the property-modified layer is properly formed.
In addition, whether the formation state of the heat-adhesive property-modified layer is appropriate is determined by using a different type of film from the base material A and a base material B that has been subjected to air corona treatment, and the thermal adhesiveness of the base material A. After the surface on which the modified layer is formed and the air corona-treated surface of the substrate B are opposed to each other and thermocompression bonded without applying an adhesive and an anchor coat agent, a test laminate is obtained, and then the test laminate It is determined by whether or not the adhesive force on the pasting surface exceeds a predetermined value.

(Example of surface modification by atmospheric pressure plasma treatment 1)
A polyamide (PA) resin film was surface-modified using an atmospheric pressure plasma treatment apparatus. The processing conditions are an irradiation time of 0.12 s, an applied power of 1.0 kW, and a frequency of 20 kHz.
Using a polyamide (PA) resin film with a thickness of 15 μm (biaxially stretched polyamide film manufactured by Kojin Co., Ltd., trade name: Bonil RX), surface modification treatment by atmospheric pressure plasma treatment was performed. A surface-modified polyamide (PA) resin film was obtained.
Next, the surface on which the heat adhesion modified layer of the polyamide (PA) resin film of surface modification example 1 was formed, and a commercially available air-corona-treated unstretched polyethylene (PE) resin film (manufactured by Tamapoly Co., Ltd.) Without facing the air-corona-treated surface of the unstretched polyethylene film, trade name: SK615P), without applying an adhesive or an anchor coating agent, it was held for 10 seconds at a temperature of 160 ° C. and a pressure of 0.4 MPa, and thermocompression bonded. A test laminate of surface modification example 1 was obtained. About the obtained test laminated body of the surface modification example 1, when the adhesive force of the bonded films was measured, the measurement result of peeling strength was 22.5N / 25.4mm.

(Example of surface modification by atmospheric pressure plasma treatment 2)
The surface modification of the surface modification example 2 was performed by performing the same operation as the surface modification example 1 except that the atmospheric pressure plasma irradiation time, applied power, and frequency were changed in a weak direction in the atmospheric pressure plasma processing apparatus. A polyamide (PA) resin film was obtained. The processing conditions are an irradiation time of 0.10 s, an applied power of 20 W, and a frequency of 13.56 MHz.
Next, using the obtained resin film of surface modification example 2, the same air corona-treated unstretched polyethylene (PE) resin film as in surface modification example 1 was used, and the same as in surface modification example 1 Bonding was performed under conditions to obtain a test laminate of surface modification example 2. The obtained test laminate of surface modification example 2 had a measured peel strength of 7.8 N / 25.4 mm.

(Example of surface modification by atmospheric pressure plasma treatment 3)
A polyethylene terephthalate (PET) resin film was surface-modified using an atmospheric pressure plasma treatment apparatus. The processing conditions are an irradiation time of 0.05 s, an applied power of 10 W, and a frequency of 13.56 MHz.
Using a polyethylene terephthalate (PET) resin film with a thickness of 12 μm (biaxially stretched polyethylene terephthalate film manufactured by Toyobo Co., Ltd., trade name: E5102), surface modification is performed by an atmospheric pressure plasma treatment apparatus. The surface-modified polyethylene terephthalate (PET) resin film of Example 3 was obtained.
Next, the surface on which the heat adhesion modified layer of the resin film of surface modification example 3 was formed, and a commercially available air-corona-treated unstretched polyethylene (PE) resin film (unstretched polyethylene film manufactured by Tamapoly Co., Ltd.) Test of surface modification example 3 by facing the air corona-treated surface of the product name: SK615P) and applying the same conditions as in surface modification example 1 without applying an adhesive and an anchor coat agent. A laminate was obtained. The test laminate of surface modification example 3 obtained had a measured peel strength of 7.9 N / 25.4 mm.

(Example of surface modification by atmospheric pressure plasma treatment 4)
The surface modification of the surface modification example 4 was performed by performing the same operation as the surface modification example 3 except that the atmospheric pressure plasma irradiation time, applied power, and frequency were changed in a weak direction in the atmospheric pressure plasma processing apparatus. A polyethylene terephthalate (PET) resin film was obtained. The processing conditions are an irradiation time of 0.01 s, an applied power of 10 W, and a frequency of 13.56 MHz.
Next, using the obtained resin film of surface modification example 4, it was bonded to a commercially available air-corona-treated unstretched polyethylene (PE) resin film under the same conditions as in surface modification example 3. A layered product of surface modification example 4 was obtained. The test laminate of surface modification example 4 obtained had a measured peel strength of 3.9 N / 25.4 mm.

(Example of surface modification by atmospheric pressure plasma treatment 5)
The cellophane film was surface modified using an atmospheric pressure plasma treatment apparatus. The processing conditions are an irradiation time of 0.15 s, an applied power of 1.2 kW, and a frequency of 30 kHz.
Using a cellophane film with a thickness of # 300 (cellophane film manufactured by Nimura Chemical Co., Ltd., trade name: Taiko PF-3), surface modification treatment was performed with an atmospheric pressure plasma treatment apparatus, and the surface of surface modification example 5 A modified cellophane film was obtained. Next, the surface on which the heat adhesion modified layer of the film of surface modification example 5 was formed, and a commercially available air-corona-treated unstretched polyethylene (PE) resin film (unstretched polyethylene film manufactured by Tamapoly Co., Ltd., Product layer: SK615P) facing the air corona-treated surface and bonding under the same conditions as surface modification example 1 without applying an adhesive and an anchor coat agent, and test lamination of surface modification example 5 Got the body. The obtained test laminate of surface modification example 5 had a measured peel strength of 2.3 N / 25.4 mm.

(Example of surface modification by atmospheric pressure plasma treatment 6)
The surface modification of the surface modification example 6 was performed by performing the same operation as the surface modification example 5 except that the atmospheric pressure plasma irradiation time, applied power, and frequency were changed in a weak direction in the atmospheric pressure plasma processing apparatus. A cellophane film was obtained. The processing conditions are an irradiation time of 0.15 s, an applied power of 300 W, and a frequency of 10 kHz.
Next, using the film of the surface modification example 6 obtained, under the same conditions as the surface modification example 5, it is bonded with a commercially available air-corona-treated unstretched polyethylene (PE) resin film, A laminate of surface modification example 6 was obtained. The test laminate of surface modification example 6 obtained had a measured peel strength of 1.3 N / 25.4 mm.

As described above, surface-modified films of surface modification examples 1 to 6 were obtained using an atmospheric pressure plasma processing apparatus.
The obtained heat-adhesive modified layers of surface modification examples 1 to 6 and an air corona-treated resin film were bonded by thermocompression bonding to obtain test laminates of surface modification examples 1 to 6.
Table 1 shows the results of measuring the peel strength of the laminated films of the test laminates of surface modification examples 1 to 6 obtained.

Next, the surface-modified films of the obtained surface modification examples 1 to 6 are opposed to the air-corona-treated thermoplastic resin film, and the molten resin film is applied without applying an adhesive and an anchor coating agent. After extruding between different films (while performing ozone treatment on the surface of the molten resin film to be combined with the first base material), it was bonded (film sand) with a cooling nip roll, and Examples 1-3 and Comparative Examples 1- 3 laminates were produced.
Moreover, in order to compare with the laminated body produced by this invention, it bonded by the film sand system which used the anchor coat agent which is a prior art, and produced the laminated body of the comparative example 4. FIG.

Example 1
The surface on which the heat-adhesive modified layer of the polyamide (PA) resin film of the surface modification example 1 is formed, and a commercially available air-corona-treated unstretched polyethylene (PE) resin film (not manufactured by Tamapoly Co., Ltd.) A stretched polyethylene film, trade name: SK615P) facing the air corona-treated surface, and without applying an adhesive and an anchor agent, a molten resin film (with the first base material of the molten resin film at 80 m / min, 320 ° C.) After extruding between the different films (while performing ozone treatment on the surfaces to be joined), the laminate of Example 1 was obtained by bonding (film sand) at 0.23 MPa with a cooling nip roll. The obtained laminate of Example 1 had a measured peel strength of 13.7 N / 25.4 mm. Moreover, after producing the packaging container of a standing pouch type | mold and a four-side seal bag using the obtained laminated body of Example 1, the various tests regarding a packaging container were done.
A standing pouch-type packaging container was produced in Example 1 and Comparative Examples 1 and 4. Moreover, the packaging container of the four-sided seal bag was produced in Examples 1-3 and Comparative Examples 1-4.

(Comparative Example 1)
Using the surface of the polyamide (PA) resin film of the surface modification example 2 on which the heat adhesion modified layer was formed and the air-corona-treated unstretched polyethylene (PE) resin film of the example 1, the example was used. Bonding with film sand was performed under the same conditions as 1 to obtain a laminate of Comparative Example 1. The obtained laminate of Comparative Example 1 had a measured peel strength value of 5.6 N / 25.4 mm. Moreover, after producing the standing pouch type | mold and the packaging container of a four-way seal bag using the obtained laminated body of the comparative example 1, the various tests regarding a packaging container were done.

(Example 2)
The surface on which the heat-adhesive modified layer of the polyethylene terephthalate (PET) resin film of the surface modification example 3 is formed, and a commercially available air-corona-treated unstretched polyethylene (PE) resin film (manufactured by Tamapoly Co., Ltd.) Using a non-stretched polyethylene film, trade name: SK615P), lamination with film sand was performed under the same conditions as in Example 1 to obtain a laminate of Example 2. The obtained laminate of Example 2 had a measured peel strength value of 6.9 N / 25.4 mm. Moreover, after producing the packaging container of a four-side seal bag using the obtained laminated body of Example 2, the various tests regarding a packaging container were done.

(Comparative Example 2)
Using the surface of the polyethylene terephthalate (PET) resin film of the surface modification example 4 on which the heat adhesion modified layer was formed and the air-corona-treated unstretched polyethylene (PE) resin film of the example 2 Bonding with film sand was performed under the same conditions as in Example 1 to obtain a laminate of Comparative Example 2. The obtained laminate of Comparative Example 2 had a measured peel strength of 2.8 N / 25.4 mm.
Moreover, after producing the packaging container of a four-sided seal bag using the obtained laminated body of the comparative example 2, the various tests regarding a packaging container were done.

(Example 3)
The surface on which the heat-adhesive modified layer of the cellophane film of the surface modification example 5 is formed, and a commercially available air-corona-treated unstretched polyethylene (PE) resin film (unstretched polyethylene film manufactured by Tamapoly Corporation, Using a product name; SK615P), lamination with film sand was performed under the same conditions as in Example 1 to obtain a laminate of Example 3. The obtained laminate of Example 3 had a measured peel strength of 2.9 N / 25.4 mm.
Moreover, after producing the packaging container of a four-side seal bag using the obtained laminated body of Example 3, the various tests regarding a packaging container were done.

(Comparative Example 3)
Using the surface of the cellophane film of the above surface modification example 6 on which the heat adhesion modified layer was formed and the air-corona-treated unstretched polyethylene (PE) resin film of the example 3, the same as the example 1 The lamination by the film sand was performed on conditions, and the laminated body of the comparative example 3 was obtained. The obtained laminate of Comparative Example 3 had a measured peel strength of 0.3 N / 25.4 mm.
Moreover, after producing the packaging container of a four-sided seal bag using the obtained laminated body of the comparative example 3, the various tests regarding a packaging container were done.

(Comparative Example 4)
After obtaining a laminate of an air corona-treated polyamide (PA) resin film and an air-corona-treated unstretched polyethylene (PE) resin film by a film sand using an anchor coating agent, the laminate is The packaging container of a standing pouch type and a four-side seal bag was used.
An air corona-treated surface of a commercially available polyamide (PA) resin film having a thickness of 15 μm (biaxially stretched polyamide film manufactured by Kojin Co., Ltd .; trade name: Bonil RX) and a commercially available air corona-treated unstretched polyethylene ( PE) Resin film (Tamapoly Co., Ltd. unstretched polyethylene film, trade name: SK615P) facing the air corona-treated surface and applying an anchor coating agent, ozone is then applied to the surface of the molten resin film to be combined with the first substrate While performing the treatment, the molten resin film was extruded between the first base material and the second base material, and then bonded (film sand) with a cooling nip roll to obtain a laminate of Comparative Example 4 through aging. It was. The obtained laminate of Comparative Example 4 had a measured peel strength of 7.2 N / 25.4 mm.
Moreover, after producing the packaging container of a standing pouch type | mold and a four-sided seal bag using the obtained laminated body of the comparative example 4, the various tests regarding a packaging container were done.

  Using the laminates of Examples 1 to 3 and Comparative Examples 1 to 4 obtained as described above, a packaging container of a standing type and a four-side sealed bag was prepared, and various tests relating to the packaging container were performed. The test results obtained are shown in Table 2.

Table 2 shows the results of various tests conducted on the standing type and the packaging containers for the four-side sealed bags produced using the laminates of Examples 1 to 3 and Comparative Examples 1 to 4 which are laminates according to the present invention.
Comparative Example 4 is a test result of a packaging container produced using a laminate produced by a film sand method using an anchor coat agent according to the prior art.
Examples 1 to 3 are test results of packaging containers produced using a laminate produced by the film sand method according to the present invention. It can be confirmed that the test results of Examples 1 to 3 which are packaging containers according to the present invention are equivalent or better than the test results of Comparative Example 4 which is a packaging container prepared by the conventional technique.
Therefore, the laminate according to the present invention has a property equivalent to or higher than that of the laminate by the film sand method using the anchor coating agent according to the prior art, and can be used as a constituent material of the packaging container without causing any problem. It is possible.

Table 3 shows a content resistance product suitability test for the packaging container of Comparative Example 4 produced by the prior art and the packaging container of Example 1 according to the present invention, filled with the contents and stored at 50 ° C. for 1 month. It is the result of having evaluated the adhesive strength of the laminated body after the storage period between.
The packaging container of Example 1 was produced using a laminate produced by a film sand method using an anchor coating agent according to a conventional conventional technique, without causing the occurrence of the delamination (peeling from the bonded surface) phenomenon. It has the same excellent durability as the packaging container.

  Table 4 shows the film sand method of Comparative Example 4, which is a packaging container produced using a laminate produced by a film sand method using an anchor coating agent according to the prior art. The amount of solvent (kg) required when processing 1,000 m. The amount of solvent required for film sand processing using an anchor coating agent according to the prior art was 2.3 (kg). On the other hand, in the case of the present invention, since an anchor coat agent is not used, a packaging container can be produced without using any solvent.

  In addition, when the test results in Table 1 and Table 2 are comprehensively determined, the adhesive force of the heat-adhesive modified layer by surface modification applied to the film using an atmospheric pressure plasma processing apparatus is appropriately determined as follows. Just control. If it does so, the film in which the heat-adhesive property modification layer by the surface modification of atmospheric pressure plasma processing suitable for implementing this invention was formed can be obtained.

(Plasma treatment for polyamide resin)
To determine the quality of the surface of the polyamide (PA) resin film on which the thermal adhesion modified layer is formed by surface modification using an atmospheric pressure plasma treatment device, surface modification of the polyamide (PA) resin film The surface on which the heat-adhesive modified layer is formed is opposed to the air-corona-treated surface of a commercially available air-corona-treated unstretched polyethylene (PE) resin film (unstretched polyethylene film manufactured by Tamapoly Co., Ltd., trade name: SK615P). The adhesive strength when heated and pressure-bonded by holding at a temperature of 160 ° C. and a pressure of 0.4 MPa for 10 seconds without applying an adhesive and an anchor coating agent is JIS K 6854-1 “adhesive peeling adhesion Strength test method Part 1: 90 ° Peeling “Atmospheric pressure so that the value measured by the measurement method is 9.8 N / 25.4 mm or more. What is necessary is just to perform surface modification using a plasma processing apparatus.

(Plasma treatment for polyethylene terephthalate resin)
In order to determine the quality of a surface on which a heat-adhesive modified layer is formed by surface modification using an atmospheric pressure plasma processing apparatus with respect to a polyethylene terephthalate (PET) resin film, the surface modification of the polyethylene terephthalate (PET) resin film is performed. The surface on which the heat-adhesive modified layer is formed according to the quality and the air-corona-treated surface of a commercially available air-corona-treated unstretched polyethylene (PE) resin film (unstretched polyethylene film manufactured by Tamapoly Co., Ltd., trade name: SK615P) Adhesive strength when heated and pressure-bonded by holding at a temperature of 160 ° C. and a pressure of 0.4 MPa for 10 seconds without applying an adhesive and an anchor coating agent to each other is JIS K 6854-1 “adhesive peeling. The value measured by the measurement method defined in “Adhesion strength test method Part 1: 90 degree peeling” is 5.9 N / 25 The surface may be modified using an atmospheric pressure plasma processing apparatus so that the thickness is 4 mm or more.

(Plasma treatment for cellophane film)
To determine the quality of the surface of the cellophane film on which the thermal adhesion modified layer has been formed by surface modification using an atmospheric pressure plasma treatment device, the thermal adhesive modified layer is formed by surface modification of the cellophane film. An adhesive and an anchor coating agent are made to face the air corona-treated surface of a commercially available air corona-treated unstretched polyethylene (PE) resin film (Tamapoly Co., Ltd. unstretched polyethylene film, trade name: SK615P). Adhesive strength when heated and pressure-bonded by holding at a temperature of 160 ° C. and a pressure of 0.4 MPa for 10 seconds without applying JIS K 6854-1 “Adhesive Peeling Adhesive Strength Test Method Part 1: 90 Surface using an atmospheric pressure plasma treatment apparatus so that the value measured by the measurement method specified in “Debonding” is 2.0 N / 25.4 mm or more. What is necessary is just to modify.

According to the present invention, the film was subjected to atmospheric pressure plasma treatment necessary to obtain a laminate bonded (or laminated by extrusion lamination) with film sand without using an adhesive and an anchor coating agent. It is possible to effectively perform the atmospheric pressure plasma treatment by determining whether or not the formation state of the thermal adhesion reforming layer of the film is good.
In addition, according to the present invention, a method for producing a laminate bonded with film sand (or laminated by extrusion lamination) without using an adhesive and an anchor coating agent, the laminate, and a package produced using the laminate A container can be obtained.
The laminated body by this invention can be used for various uses, such as a decorative sheet, an optical film, a protective film, and a packaging container.
In addition, the packaging container prepared using the laminate according to the present invention includes liquid seasonings, liquid detergents, liquid bleaches, liquid waxes, hair care products (including shampoos, rinses, conditioners, etc.), chemicals, liquids It can be used for packaging containers for various liquid products such as cosmetics and packaging containers for refilling, as well as various packaging containers for foods, electronic parts, medical parts, medical equipment parts, precision machine parts and the like.
Further, according to the present invention, it is possible to produce a laminate and a packaging container using the same without using an adhesive and an anchor coating agent, that is, without using any organic solvent. It is effective as an energy saving measure.

DESCRIPTION OF SYMBOLS 1 ... 1st base material used as the object of surface modification processing, 2 ... Thermal-adhesion modification layer, 3 ... Printing layer, 5 ... 1st base material which carried out surface modification processing, 6 ... Surface modification processing Second target substrate, 7 ... Air corona treated surface (or heat adhesion modified layer), 8 ... Second base material subjected to surface modification treatment, 10 ... Laminate by film sand of the present invention, 11 ... Laminated body by extrusion lamination of the present invention, 20 ... Laminated body having a printed layer of the present invention, 21 ... Roll body of first base material to be subjected to surface modification treatment, 22 ... Subject to surface modification treatment 2nd roll body, 23 ... atmospheric pressure plasma treatment apparatus, 24 ... air corona treatment apparatus, 25 ... cooling nip roll, 26 ... extrusion die, 27 ... molten resin film, 28 ... laminated roll body, 29a, 29b , 29c ... roller, 40 ... laminate according to the prior art, 41 ... first Wood, 42 ... second substrate, 43, 44 ... air corona treated surface, 45 ... adhesive layer.

Claims (15)

  A method of manufacturing a laminate in which a first base material and a second base material made of different types of thermoplastic resin films or cellophane films are bonded, each having a thickness of 10 to 500 μm and a length of 3 The first base material fed out from the roll body wound with the first base material and the second base material, each of which is a long film of 10,000 m, is obtained by an atmospheric pressure plasma processing apparatus. The second substrate has a surface on which a heat-adhesive modified layer is formed by surface modification, and the second substrate has a surface on which a heat-adhesive modified layer is formed by surface modification by an atmospheric pressure plasma processing apparatus, or air corona treatment A surface having an air corona treatment using an apparatus, a surface on which the heat-adhesive modified layer of the first substrate is formed, and a surface on which the heat-adhesive modified layer of the second substrate is formed, or An air corona-treated surface is opposed to the first substrate and the first substrate Without applying an adhesive and an anchor coating agent between the base material and the extruded resin film, the molten resin film is extruded and subjected to ozone treatment on the surface of the molten resin film to be joined with the first base material. The manufacturing method of the laminated body characterized by carrying out continuous bonding in. A method for producing a laminate in which a first base material made of different types of thermoplastic resin films or cellophane films and a molten resin film are laminated, wherein the first base material and the molten resin film are laminated. The first base material on which the thermal adhesion modified layer is formed by surface modification of the film using an atmospheric pressure plasma processing apparatus in advance, and a different kind of thermoplastic resin film from the first base material Then, using a third base material that has been subjected to air corona treatment, the surface of the first base material on which the heat-adhesive property-modified layer is formed and the air corona treatment surface of the third base material are made to face each other. The test laminate is obtained by thermocompression bonding without applying the adhesive and the anchor coating agent, and then the adhesive force on the bonding surface of the test laminate is measured to thermally bond the first substrate. check the quality of the state of formation of the sexual modified layer, thickness Is 10 to 500 μm, and the first substrate fed out from the roll body wound with the first substrate made of a long film having a length of 3 to 10,000 m is atmospheric pressure plasma. An adhesive and an anchor coating agent are provided on the surface of the first base material on which the heat-adhesive modified layer is formed by surface modification by a processing apparatus. The laminated resin film is characterized in that the molten resin film is extruded without being coated and continuously bonded with a cooling nip roll while performing ozone treatment on the surface of the molten resin film to be bonded to the first base material. Production method. Upon laminating the second substrate and the first substrate in advance, the first heat-adhesive modifying layer by surface modification are formed of films using an atmospheric pressure plasma treatment apparatus And a third base material, which is a different type of thermoplastic resin film from the first base material and subjected to air corona treatment, After the formed surface and the air corona-treated surface of the third substrate are opposed to each other and thermocompression bonded without applying an adhesive and an anchor coat agent, a test laminate is obtained, and then the test laminate is pasted. by measuring the adhesive strength of mating surface, a manufacturing method of a laminate according to claim 1, quality of the state of formation of the heat-adhesive modifying layer of the first substrate, characterized in that it is confirmed. When the first substrate is a polyamide (PA) resin film, an unstretched polyethylene (PE) resin film treated with air corona is used as the third substrate, and the temperature is 160 ° C. and the applied pressure is 0.4 MPa. The adhesive strength when heated and pressure-bonded for 10 seconds is JIS K 6854-1, “Adhesive Peeling Adhesive Strength Test Method Part 1: 90 degree peeling” and the value measured by the measuring method is 9 Confirm that it is 8N / 25.4mm or more,
When the first substrate is a polyethylene terephthalate (PET) resin film, an unstretched polyethylene (PE) resin film that has been subjected to air corona treatment is used as the third substrate, and the temperature is 160 ° C. and the applied pressure is 0. The adhesive force when held at 4 MPa for 10 seconds and thermocompression bonded is the value measured by the measurement method specified in JIS K 6854-1 “Adhesive Peeling Adhesive Strength Test Method Part 1: 90 degree peeling” 5.9N / 25.4mm or more is confirmed,
When the first substrate is a cellophane film, an air-corona-treated unstretched polyethylene (PE) resin film is used as the third substrate and held at a temperature of 160 ° C. and a pressure of 0.4 MPa for 10 seconds. The adhesive strength when thermocompression bonding was performed was 2.0 N / 25 as measured by the measurement method defined in JIS K 6854-1, “Adhesive Peeling Adhesive Strength Test Method Part 1: 90 ° Peeling”. It confirms that it will be 4 mm or more, The manufacturing method of the laminated body of Claim 3 characterized by the above-mentioned.   5. The aging step of allowing the laminate to stand at room temperature for 10 days to 1 month, or at 40 to 60 ° C. for 1 to 3 days after the bonding step, according to claim 1. A manufacturing method of a layered product. The first substrate is made of a film group consisting of polyethylene terephthalate (PET), polyamide (PA), polyethylene naphthalate (PEN), polyacrylonitrile (PAN), polycarbonate (PC), polyimide (PI), and cellophane. 2. The selected one type, wherein the second base material is unstretched polyethylene (PE) or a coextruded film of unstretched polyethylene and unstretched polypropylene (PE / CPP). The manufacturing method of the laminated body of 3 or 4 .   The first substrate is made of a film group consisting of polyethylene terephthalate (PET), polyamide (PA), polyethylene naphthalate (PEN), polyacrylonitrile (PAN), polycarbonate (PC), polyimide (PI), and cellophane. The method for producing a laminate according to any one of claims 1 to 5, wherein the molten resin is one kind selected and the molten resin is polyethylene (PE).   The method for producing a laminate according to any one of claims 1 to 7, wherein a printed layer is formed on at least one surface of the film serving as the first substrate.   The laminated body manufactured by the manufacturing method of the laminated body in any one of Claim 1 to 8. Claim 1, using a laminate produced by the method for producing a laminate according to 3, 4 or 6, said second substrate is formed by produced to an inner surface side as a sealant layer Characteristic packaging container. Using a laminate produced by the method for producing a laminate according to claim 2, wherein the packaging container molten resin film is characterized by comprising been produced to an inner surface side as a sealant layer.   A laminate in which a first base material and a second base material made of different types of thermoplastic resin films or cellophane films are bonded, wherein the first base material is polyethylene terephthalate (PET), polyamide (PA), polyethylene naphthalate (PEN), polyacrylonitrile (PAN), polycarbonate (PC), polyimide (PI), and one type selected from cellophane, and the second substrate is , Unstretched polyethylene (PE), or a coextruded film of unstretched polyethylene and unstretched polypropylene (PE / CPP), and the first substrate and the second substrate have a thickness of 10 to 500 μm, It consists of a long film having a length of 3 to 10,000 m, and the first substrate is an atmospheric pressure plastic on the bonding surface of the laminate. The surface on which the heat-adhesive modified layer is formed by the surface modification by the processing apparatus, and the second substrate has the surface on which the heat-adhesive modified layer is formed by the surface modification by the atmospheric pressure plasma processing apparatus. Or a surface having an air corona-treated surface using an air corona treatment apparatus, a surface on which the heat-adhesive modified layer of the first substrate is formed, and a heat-adhesive modified layer of the second substrate are formed Using the adhesive and the anchor agent, the surface to be joined with the first substrate of the molten resin film is subjected to ozone treatment through the molten resin film while the surface or the air corona-treated surface is opposed The laminated body characterized by not being bonded. A laminated body in which a first base material and a molten resin film made of different kinds of thermoplastic resin films or cellophane films are laminated, and when the first base material and the molten resin film are laminated, The first base material on which a thermal adhesion modified layer is formed by surface modification of the film using an atmospheric pressure plasma processing apparatus, and a thermoplastic resin film of a different type from the first base material, Using a third base material that has been subjected to air corona treatment, the surface of the first base material on which the heat-adhesive property-modified layer is formed and the air corona treatment surface of the third base material are made to face each other and bonded. After applying a thermocompression bonding without applying an agent and an anchor coating agent to obtain a test laminate, the adhesive strength on the bonding surface of the test laminate is measured to improve the thermal adhesion of the first substrate. quality of the state of formation of layers has been seen, the first Was selected from the group of films consisting of polyethylene terephthalate (PET), polyamide (PA), polyethylene naphthalate (PEN), polyacrylonitrile (PAN), polycarbonate (PC), polyimide (PI), and cellophane. 1 type, the molten resin is polyethylene (PE), the first base material is a long film having a thickness of 10 to 500 μm and a length of 3 to 10,000 m, On the bonding surface of the laminated body, the first base material has a surface on which a thermal adhesion modified layer is formed by surface modification by an atmospheric pressure plasma processing apparatus, and the thermal adhesion modification of the first base material is performed. On the surface on which the porous layer is formed, an adhesive and an anchor agent are not used, and the surface of the molten resin film to be combined with the first base material is subjected to ozone treatment and laminated. A laminate characterized by the above. A packaging container manufactured using the laminate according to claim 12 so that the second base material is an inner surface side as a sealant layer. A packaging container produced by using the laminate according to claim 13 so that the molten resin film becomes an inner surface side as a sealant layer.

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