JP2011143586A - Method for manufacturing packaging material laminate, packaging material laminate, and package using the packaging material laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing a packaging material laminate, laminating a sealant layer without using an adhesive and an anchor coating agent while reducing the warp and curl of the laminate, and to provide the packaging material laminate and a package produced using the packaging material laminate. <P>SOLUTION: Second base materials 1, 1 which are thermoplastic resin films of the different kind from a first base material 3 and having heat sealing property are disposed on both sides of the first base material 3 made of a thermoplastic resin film. A heat-adhesive modified layer is formed on one of the lamination surface of the first base material 3 and the lamination surface of the second base material 1 by surface modification using an atmospheric pressure plasma treating apparatus, and a surface modified layer is formed on the other lamination surface by air corona treatment. The formed surface of the heat-adhesive modified layer and the formed surface of the surface modified layer of the first base material 3 and second base material 1 are placed to face each other and laminated by heat-bonding under pressure without applying the adhesive and anchor coating agent. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

The present invention relates to a method for manufacturing a packaging material laminate using a surface-modified resin film, a packaging material laminate, and a packaging body using the same. More specifically, by not using an adhesive and an anchor coating agent, it is a clean, VOC (volatile organic compound) that does not generate low molecular components due to the adhesive and the anchor coating agent, which can be a source of contamination to the contents. Compound) is completely eliminated, the manufacturing method of the packaging material laminate, which is excellent in environmental measures and energy saving measures, and has less warping and curling of the laminate, the packaging material laminate, and the packaging produced using the packaging material laminate is there.
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 Packaging containers and refill packaging containers for products containing various liquids such as cosmetics or liquids such as moisture, and various packaging containers for food, electronic parts, medical parts, medical equipment parts, precision machine parts, etc. Widely used for.

Traditionally, packaging for storing, storing and transporting hair care products, household products, chemicals, foods, electronic parts, medical parts, medical equipment parts, precision machine parts, etc. has a sealant layer on the inner surface. A flexible packaging bag or packaging container (hereinafter referred to as a packaging body) in which the peripheral edge of the synthetic resin film is heat-sealed is used.
As a packaging material laminate used for such a packaging, for example, a laminate having a configuration such as polyamide (PA) resin film / unstretched polyethylene (PE) resin film has been widely used.
In the case of manufacturing this laminate, the resin film is usually bonded by a dry lamination method using an adhesive.

In addition, in the prior art, a film that uses an anchor coating agent as a method different from the dry laminating method that uses an adhesive to combine two or more types of resin films and bond the resin films together. A sand method or an extrusion laminating method may be used.
Adhesive strength may be insufficient unless an adhesive or anchor coating agent is used to bond the resin films together. However, the dry laminating method using an adhesive, the film sand method using an anchor coating agent, and the extrusion laminating method have problems in terms of environmental measures and energy saving measures due to the use of organic solvents. The low molecular weight component resulting from the adhesive and the anchor coat agent may react with the contents filled in the packaging bag to cause contamination of the contents or adversely affect the contents of the contents.
In addition, when polyethylene-based resin is melt-extruded to the sealant layer by extrusion laminating method, polyethylene-based resin may be decomposed and polyethylene odor may adhere, which is used to fill foods and other contents that dislike odor. There was a problem in using it as a packaging material laminate.
For this reason, as a more preferable method for producing a packaging material laminate, 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 1 to 3). 7).
In Patent Document 1, 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 2, 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, or 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 3, 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 the oxygen concentration is 0.1 vol. % Or less), a surface treatment method for a synthetic resin is described.
Patent Document 4 discloses the number of nitrogen and carbon atoms on the surface of a substrate film by ESCA method by corona discharge treatment in nitrogen gas (oxygen concentration of 3 vol% or less), carbon dioxide gas or a mixed gas atmosphere of nitrogen / carbon dioxide gas. 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 5 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 resin to be laminated is subjected to low-temperature plasma treatment using a scanning glow discharge plasma apparatus and then laminated by thermocompression bonding.
Patent Document 6 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 have a melting point of the substrate or lower. A bonding apparatus and a bonding method for bonding by pressure bonding at a temperature are shown.
In Patent Document 7, 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 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 1 and 2, the adhesive 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 3 and 4 describe methods 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 5, 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 6 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, so that it is intended for industrial use. I can't.

Patent Document 7 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, are formed on the film surface and can be firmly laminated and bonded at low temperatures. No definition of criteria to judge 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.

  In addition, the dry laminating method using an adhesive, the film sand method using an anchor coating agent, and the extrusion laminating method use organic solvents, which may cause the migration of residual solvents and low molecular components. There was a problem that the influence of contamination was inevitable. For these reasons, in producing a packaging material laminate by laminating resin films, it is required to reduce the amount of adhesive and anchor coat agent used as much as possible.

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.
In addition, when the different types of films are bonded to each other by the dry lamination method, the film sand method using an anchor coating agent, the extrusion lamination method, or the heat lamination according to the conventional technology, the obtained laminate does not warp or curl. In some cases, the appearance is inferior, or problems may occur in subsequent processes such as winding in the manufacturing process of the laminate or manufacturing process of the package.
As described above, in the prior art, a method for producing a packaging material laminate in which different types of films are laminated without using an adhesive and an anchor coating agent, and the laminate is less warped and curled, the packaging material laminate, and the same The package produced using the sac was not known.

  The present invention has been made in view of the above. That is, the object of the present invention is to use a clean, VOC (volatile), which does not generate low molecular components due to the adhesive and the anchor coat agent, which can be a source of contamination to the contents by not using the adhesive and the anchor coat agent. The production method of a packaging material laminate, which is excellent in environmental measures and energy saving measures, and has less warping and curling of the laminate, a packaging material laminate, and a package produced using the same The issue is to provide.

In the present invention, in order to solve the above-described problem, a second type of thermoplastic resin film different from the first base material and having heat sealability is provided on both surfaces of the first base material made of the thermoplastic resin film. And a thermoplastic resin film adjacent to the base material having the heat-sealability, and an adhesive and an anchor coating agent. Provided is a method for producing a packaging material laminate having less warping and curling which are bonded by thermocompression bonding without being applied.
On the bonding surface of the thermoplastic resin film, a thermal adhesion modified layer is formed by surface modification using an atmospheric pressure plasma processing apparatus, and on the bonding surface of the base material having the heat sealability, an air corona treatment ( Provided is a method for producing a packaging material laminate having less warping and curling, which is obtained by subjecting unstretched polypropylene to atmospheric pressure plasma treatment.
In addition, a thermoadhesive modified layer is formed by surface modification using an atmospheric pressure plasma processing apparatus on both the bonding surface of the thermoplastic resin film and the bonding surface of the base material having heat sealability. Provided is a method for producing a packaging material laminate with less warping and curling.
In the present invention, the packaging material laminate cut to a size of 10 cm × 10 cm (that is, a square shape with a side of 10 cm) is placed on a horizontal table, and the four corners of the packaging material laminate are lifted from the table. A case where the maximum value of the distance is 42 mm or less is defined as a “packaging material laminate with less warping and curling”.

In the present invention, a thermoplastic resin film of a different type from the first base material, which is bonded to both surfaces of the first base material (for convenience of explanation, one is called the front surface and the other is called the back surface), and has a heat seal property In the case where the second base material is unstretched polyethylene (PE), for example, the polyethylene (PE) to be bonded to the front surface and the back surface of the first base material is not the same type, and the first base material In some cases, polyethylene (PE) having different densities of polyethylene (PE) to be bonded to the front surface and the back surface is bonded.
Moreover, in order to solve the said subject, this invention is a thermoplastic resin film of the kind different from a said 1st base material on both surfaces of the 1st base material which consists of a thermoplastic resin film, and has heat-sealability. It is a manufacturing method of the packaging material laminated body formed by arrange | positioning and bonding a 2nd base material, Comprising: One bonding surface of the said 1st base material is set to 1A surface, and the other bonding surface is set to 1B surface. The bonding surfaces of the second substrates to be bonded to each other are the 2A surface and the 2B surface, and both the 1A surface and the 1B surface, which are the bonding surfaces of the first substrate, are subjected to atmospheric pressure plasma treatment. A heat-adhesive modified layer is formed by surface modification using an apparatus, and the 2A and 2B surfaces, which are the bonding surfaces of the second substrate, are formed by surface modification using an atmospheric pressure plasma processing apparatus. The first adhesive layer formed with a heat-adhesive modified layer or a surface modified layer formed by air corona treatment Material and the second base material, the 1A surface and the 2A surface, and the 1B surface and the 2B surface of the first base material and the second base material are opposed to each other, and an adhesive and an anchor coating agent are prepared. Provided is a method for producing a packaging material laminate with less warping and curling, characterized by being bonded by thermocompression bonding without coating.

  Moreover, in order to solve the said subject, this invention is a thermoplastic resin film of the kind different from a said 1st base material on both surfaces of the 1st base material which consists of a thermoplastic resin film, and has heat-sealability. It is a manufacturing method of the packaging material laminated body formed by arrange | positioning and bonding a 2nd base material, Comprising: One bonding surface of the said 1st base material is set to 1A surface, and the other bonding surface is set to 1B surface. The bonding surfaces of the second base material to be bonded to each other are the 2A surface and the 2B surface, and either one of the 1A surface and the 1B surface, which is the bonding surface of the first base material, A thermal adhesion modified layer is formed by surface modification using an atmospheric pressure plasma processing apparatus, and a surface modified layer by air corona treatment is formed on the other surface. Surface modification by air corona treatment is performed on the bonding surface of the second base material bonded to the bonding surface on which the modified layer is formed. Is formed, or a heat-adhesive modified layer is formed by surface modification using an atmospheric pressure plasma processing apparatus, and is bonded to the bonding surface on which the surface modified layer of the first substrate is formed The first base material and the second base material, in which a thermal adhesion modified layer is formed on the bonding surface of the second base material by surface modification using an atmospheric pressure plasma processing apparatus. And 1A side and 2A side and 1B side and 2B side of the first base material and the second base material are opposed to each other, and thermocompression bonding is performed without applying an adhesive and an anchor coat agent. And a method for producing a packaging material laminate with less warping and curling.

  Moreover, in order to solve the said subject, this invention is a thermoplastic resin film of the kind different from a said 1st base material on both surfaces of the 1st base material which consists of a thermoplastic resin film, and has heat-sealability. It is a manufacturing method of the packaging material laminated body formed by arrange | positioning and bonding a 2nd base material, Comprising: One bonding surface of the said 1st base material is set to 1A surface, and the other bonding surface is set to 1B surface. The surface of the second base material to be bonded to each other is the 2A surface and 2B surface, and both the 1A surface and the 1B surface, which are the surface of the first base material, are air corona-treated surfaces. A modified layer is formed, and a thermal adhesive modified layer is formed on both the 2A surface and the 2B surface, which are the bonding surfaces of the second base material, by surface modification using an atmospheric pressure plasma processing apparatus. The first base material and the second base material are prepared, and the 1A surface of the first base material and the second base material A manufacturing method of a packaging material laminate with less warping and curling, characterized in that the A side and the 1B side and the 2B side face each other and are bonded by thermocompression bonding without applying an adhesive and an anchor coating agent. provide.

  In the method for producing a laminate, the first base material and the second base material are bonded together in advance by surface modification of a resin film using an atmospheric pressure plasma processing apparatus. The atmospheric pressure plasma treatment effect of the second base material and / or the first base material on which the property modifying layer is formed, and the same or different kind of thermoplastic resin film and air corona treatment. Using a judgment reference film, the surface of the second base material and / or the first base material on which the heat-adhesion modified layer is formed and the air corona treatment surface of the judgment reference film face each other for adhesion After applying the thermocompression bonding without applying the agent and the anchor coat agent to obtain the test laminate, the adhesive strength on the bonding surface of the test laminate is measured, and the second substrate and / or the first Confirm the quality of the thermal adhesive reforming layer on the base material It is preferable to.

When the base material on which the heat-adhesive modified layer is formed using an atmospheric pressure plasma processing apparatus is a polyamide (PA) resin film, an air-corona-treated unstretched polyethylene (PE) resin film as the determination reference film The adhesive strength when heated and pressed by holding for 10 seconds at a temperature of 160 ° C. and a pressure of 0.4 MPa is JIS K 6854-1 “Adhesive Peeling Adhesive Strength Test Method Part 1: 90 degree peeling” Confirmed that the value measured by the measurement method specified in the above is 9.8 N / 25.4 mm or more,
When the base material on which the heat-adhesive modified layer is formed using an atmospheric pressure plasma processing apparatus is an unstretched polyethylene (PE) resin film, an air corona-treated polyethylene terephthalate (PET) resin as the determination reference film Using a film, 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 is JIS K 6854-1 “Adhesive Peeling Adhesive Strength Test Method Part 1: 90 degree peeling. Confirmed that the value measured by the measurement method stipulated in "" is 5.9N / 25.4mm or more,
When the base material on which the heat-adhesive modified layer is formed using an atmospheric pressure plasma treatment apparatus is a polyethylene terephthalate (PET) resin film, an unstretched polyethylene (PE) resin treated with air corona as the determination reference film Using a film, 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 is JIS K 6854-1 “Adhesive Peeling Adhesive Strength Test Method Part 1: 90 degree peeling. Confirmed that the value measured by the measurement method stipulated in "" is 5.9N / 25.4mm or more,
When the base material on which the heat-adhesive modified layer is formed using an atmospheric pressure plasma processing apparatus is a polyvinyl chloride (PVC) resin film, uncorrelated polyethylene (PE) that has been subjected to air corona treatment as the determination reference film Adhesive strength when a resin film is used and held for 10 seconds at a temperature of 140 ° C. and a pressure of 0.4 MPa is JIS K 6854-1 “Adhesive Peeling Bond Strength Test Method Part 1: 90 ° Confirm that the value measured by the measurement method specified in “peeling” is 3.9 N / 25.4 mm or more,
When the base material on which the heat-adhesive modified layer is formed using an atmospheric pressure plasma processing apparatus is an ethylene-vinyl alcohol copolymer (EVOH) resin film, an air-corona-treated unstretched film as the determination reference film Adhesive strength when a polyethylene (PE) resin film is used for 10 seconds by holding at a temperature of 160 ° C. and a pressure of 0.4 MPa for 10 seconds is JIS K 6854-1 “Adhesive peel adhesion strength test method 1 Part: 90 degree peeling ”, and confirm that the value measured by the measuring method is 5.9 N / 25.4 mm or more,
When the base material on which the heat adhesion modified layer is formed using an atmospheric pressure plasma treatment apparatus is an unstretched polypropylene (CPP) resin film, an air corona-treated polyethylene terephthalate (PET) resin as the determination reference film Using a film, the adhesive strength when heated and pressure-bonded by holding at a temperature of 190 ° C. and a pressure of 0.4 MPa for 10 seconds is JIS K 6854-1 “Adhesive Peeling Adhesive Strength Test Method Part 1: 90 degree peeling It is preferable to confirm that the value measured by the measuring method specified in “4” is 5.9 N / 25.4 mm or more.

The first base material is polyethylene terephthalate (PET), polyamide (PA), expanded polypropylene (OPP), polyethylene naphthalate (PEN), polyacrylonitrile (PAN), polycarbonate (PC), polyimide (PI), polychlorinated. One type selected from the group consisting of vinyl (PVC) and ethylene-vinyl alcohol copolymer (EVOH), and the second base material is unstretched polyethylene (PE), unstretched polypropylene (CPP) One type or two types selected from the group consisting of coextruded films of unstretched polyethylene and unstretched polypropylene (PE / CPP) are preferred.
The first base material is a laminate film in which a thermoplastic resin film is laminated on both sides, and the thermoplastic resin film on both sides of the first base material is polyethylene terephthalate (PET) or polyamide (PA). , Expanded polypropylene (OPP), polyethylene naphthalate (PEN), polyacrylonitrile (PAN), polycarbonate (PC), polyimide (PI), polyvinyl chloride (PVC), ethylene-vinyl alcohol copolymer (EVOH) And the second base material is unstretched polyethylene (PE), unstretched polypropylene (CPP), co-extruded film of unstretched polyethylene and unstretched polypropylene (PE / One or two selected from the group consisting of (CPP) It is preferred.

  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. Thereby, the adhesive force can be increased.

Moreover, this invention provides the packaging material laminated body with few curvature and curl manufactured by the manufacturing method of the packaging material laminated body with few said curvature and curl.
Moreover, this invention is manufactured so that either one of the said 2nd base material which has the said heat-sealability may become an inner surface side as a sealant layer using the packaging material laminated body with few said curvature and curls. Provided is a package characterized by the above.

  In the present invention, a second base material, which is a thermoplastic resin film of a different type from the first base material and has heat sealability, is attached to both surfaces of the first base material made of a thermoplastic resin film. The 1st bonding surface of the said 1st base material is 1A surface, the other bonding surface is made into 1B surface, and the bonding surface of the said 2nd base material bonded to each is 2A surface 2B surface, both the 1A surface and 1B surface, which are the bonding surfaces of the first base material, are formed with a thermal adhesion modified layer by surface modification using an atmospheric pressure plasma processing apparatus, On the 2A and 2B surfaces, which are the bonding surfaces of the second base material, a thermal adhesion modified layer is formed by surface modification using an atmospheric pressure plasma processing apparatus, or surface modification by air corona treatment. A first layer, a second surface, and a first surface of the first base material and the second base material, B surface and is opposed, to provide an adhesive and warp or curl less packaging material laminate, characterized in that they are stuck by heat pressing without applying the anchor coating agent.

  In the present invention, a second base material, which is a thermoplastic resin film of a different type from the first base material and has heat sealability, is attached to both surfaces of the first base material made of a thermoplastic resin film. The 1st bonding surface of the said 1st base material is 1A surface, the other bonding surface is made into 1B surface, and the bonding surface of the said 2nd base material bonded to each is 2A surface 2B surface, and either the 1A surface or the 1B surface, which is the bonding surface of the first base material, is subjected to surface modification using an atmospheric pressure plasma processing apparatus to form a thermal adhesion modified layer. The second substrate is bonded to the bonding surface on which the surface-modified layer by air corona treatment is formed on the other surface and the heat-adhesive modified layer of the first substrate is formed. A surface modification layer by air corona treatment is formed on the bonding surface of, or surface modification using an atmospheric pressure plasma treatment device An atmospheric pressure plasma treatment is performed on the bonding surface of the second base material, which is bonded to the bonding surface on which the surface modified layer of the first base material is formed. A heat-adhesive modified layer is formed by surface modification using an apparatus, and the 1A surface and 2A surface, and the 1B surface and 2B surface of the first substrate and the second substrate face each other. And the packaging material laminated body with few curvature and curl characterized by being bonded by thermocompression bonding, without apply | coating an adhesive agent and an anchor coating agent.

  In the present invention, a second base material, which is a thermoplastic resin film of a different type from the first base material and has heat sealability, is attached to both surfaces of the first base material made of a thermoplastic resin film. The 1st bonding surface of the said 1st base material is 1A surface, the other bonding surface is made into 1B surface, and the bonding surface of the said 2nd base material bonded to each is 2A surface The surface modification layer by the air corona treatment is formed on both the 1A surface and the 1B surface, which are the bonding surfaces of the first base material, and the bonding surface of the second base material. On both the 2A surface and the 2B surface, a thermal adhesion modified layer is formed by surface modification using an atmospheric pressure plasma processing apparatus, and the first substrate and the second substrate are 1A surface and 2A surface, and 1B surface and 2B surface face each other, and heat press bonding without applying adhesive and anchor coat agent The combined to provide a warp or curl less packaging material laminate, characterized in that.

The first base material is polyethylene terephthalate (PET), polyamide (PA), expanded polypropylene (OPP), polyethylene naphthalate (PEN), polyacrylonitrile (PAN), polycarbonate (PC), polyimide (PI), polychlorinated. One type selected from the group consisting of vinyl (PVC) and ethylene-vinyl alcohol copolymer (EVOH), and the second base material is unstretched polyethylene (PE), unstretched polypropylene (CPP) One type or two types selected from the group consisting of coextruded films of unstretched polyethylene and unstretched polypropylene (PE / CPP) are preferred.
The first base material is a laminate film in which a thermoplastic resin film is laminated on both sides, and the thermoplastic resin film on both sides of the first base material is polyethylene terephthalate (PET) or polyamide (PA). , Expanded polypropylene (OPP), polyethylene naphthalate (PEN), polyacrylonitrile (PAN), polycarbonate (PC), polyimide (PI), polyvinyl chloride (PVC), ethylene-vinyl alcohol copolymer (EVOH) And the second base material is unstretched polyethylene (PE), unstretched polypropylene (CPP), co-extruded film of unstretched polyethylene and unstretched polypropylene (PE / One or two selected from the group consisting of (CPP) It is preferred.

  Moreover, this invention is manufactured so that either one of the said 2nd base material which has the said heat-sealability may become an inner surface side as a sealant layer using the packaging material laminated body with few said curvature and curls. Provided is a package characterized by the above.

According to the present invention, since the adhesive and the anchor coating agent are not used to bond the heat seal layer that is the innermost layer of the package, the adhesive and the anchor can be a source of contamination to residual solvents and contents. Since the generation of low-molecular components due to the coating agent is not accompanied, the influence of contamination on the contents filled in the package can be reduced.
In addition, since the adhesive and the anchor coat agent are not used to bond the heat seal layer that is the innermost layer of the package, the liquid in which the adhesive and the anchor coat agent are filled in the package as in the prior art It is possible to reduce the occurrence of adverse effects on the components of the contents by reacting with the contents, for example, the decomposition or reduction of medicinal components.
Moreover, according to this invention, it is the 2nd base material which is a thermoplastic resin film of the kind different from the said 1st base material on both surfaces of the 1st base material which consists of a thermoplastic resin film, and has heat-sealing property Therefore, the packaging material laminate can be manufactured in which distortion due to thermal shrinkage is equalized and the laminate is less warped or curled.

It is a schematic sectional drawing which shows the 1st example of the packaging material laminated body concerning this invention. It is a schematic sectional drawing which shows the 2nd example of the packaging material laminated body concerning this invention. It is a schematic sectional drawing which shows an example of the packaging material laminated body by a prior art.

Hereinafter, the present invention will be described with respect to preferred embodiments.
1 and 2 are schematic cross-sectional views showing an example of a packaging material laminate according to the present invention. A second base material 1 which is a thermoplastic resin film of a different type from the first base material 3 and has heat sealability is bonded to both surfaces of the first base material 3 made of a thermoplastic resin film. On one surface of the packaging material laminates 10 and 11 with less warping and curling, in order from the top, a second base material 1 having heat sealability, a first base material 3 made of a thermoplastic resin film, The second base material 1 having heat sealability is laminated at least, and the thermoplastic resin film 3 and the base material 1 having heat sealability are applied without applying an adhesive and an anchor coating agent. It is the packaging material laminated body 10 and 11 with few curvature and curl formed by thermocompression bonding.

  In the packaging material laminate 10 with less warping and curling according to the first example shown in FIG. 1, although not particularly shown, for example, the second base material 1 and the first base material 3 having the lower heat sealability, A printing layer can be provided between the two.

In the packaging material laminate 11 with less warping and curling according to the second example shown in FIG. 2, an aluminum laminate film 5 having a heat sealing property or an easy peel property is separately thermocompression-bonded in order to provide light shielding properties and barrier properties. Is bonded to the second base material 1 having heat sealability. Although not particularly shown, for example, a printing layer can be provided between the other resin film 5 and the second base material 1 having heat sealability.
In addition, the present invention is not limited to the above example, and one selected from the group consisting of a metal foil, a metal or metal oxide vapor deposition film, and a resin composition layer having gas barrier properties in the laminate. One or more gas barrier layers may be provided.

An atmospheric pressure plasma processing apparatus is used for either the bonding surface 2 of the first base material 3 made of the thermoplastic resin film 3 or the bonding surface 2 of the second base material 1 having heat sealability. The heat-adhesive modified layer is formed by the surface modification, and the surface modified layer by the air corona treatment is formed on the other surface. The bonding surface 2 is bonded by thermocompression bonding without applying an adhesive and an anchor coating agent.
The surface of the first substrate 3 made of the thermoplastic resin film 3 and the second substrate 1 having heat sealability, on which the heat-adhesive modified layer is formed, and the surface modified layer are formed. A packaging material with less warping and curling according to the present invention by performing thermocompression bonding while keeping it at a predetermined heating temperature, pressure and time without applying an adhesive and an anchor coating agent with the surface facing each other. Bonding between the first base material 3 and the second base material 1 in the laminates 10 and 11 can be obtained.

  Moreover, the atmospheric pressure plasma processing apparatus was used for both the bonding surface 2 of the first base material 3 made of the thermoplastic resin film 3 and the bonding surface 2 of the second base material 1 having heat sealability. A surface of the first base material 3 made of the thermoplastic resin film 3 on which the heat-adhesive modified layer is formed by surface modification and a surface on which the heat-adhesive modified layer is formed and a second base having heat sealability Thermocompression bonding is performed with the surface of the material 1 facing the surface on which the heat-adhesive property-modified layer is formed being held at a predetermined heating temperature, pressure, and time without applying an adhesive and an anchor coating agent. Thereby, joining of the 1st base material 3 and the 2nd base material 1 in packaging material laminated bodies 10 and 11 with few curvature concerning this invention and curl can also be obtained.

The first substrate 3 made of a thermoplastic resin film includes a polyethylene terephthalate (PET) resin film, a polyamide (PA) resin film, an expanded polypropylene (OPP), a polyethylene naphthalate (PEN) resin film, and a polyacrylonitrile (PAN). Examples thereof include a resin film, a polycarbonate (PC) resin film, a polyimide (PI) resin film, polyvinyl chloride (PVC), and an ethylene-vinyl alcohol copolymer (EVOH).
Moreover, as the 2nd base material 1 which has heat-sealability, an unstretched polyethylene (PE) resin film or an unstretched polypropylene (CPP) resin film, a co-extrusion film (PE / CPP) of unstretched polyethylene and unstretched polypropylene Etc.
Examples of the metal foil serving as the gas barrier layer include aluminum foil and stainless steel foil. In addition, examples of the metal or metal oxide to be a vapor deposition film having gas barrier properties include aluminum, silica, and alumina. In addition, as the resin composition having gas barrier properties, various commercially available products (for example, vinylidene chloride coat, acrylic acid polymer coat, and organic / inorganic hybrid coat (coating agent in which an organic compound and an inorganic compound are hybridized)) are available (for example, For example, a resin having gas barrier properties and fine particles such as colloidal silica dispersed therein, or a commercially available film with coating can be used.
And in the packaging material laminated bodies 10 and 11 with few curvature and curl, the 2nd base material 1 which has heat-sealability, and the 1st base material 3 which consists of a thermoplastic resin film are an adhesive agent and an anchor coating agent. It is laminated without using.
Since the second base material 1 having heat sealability is laminated on the packaging material laminates 10 and 11 with less warping and curling, the packaging material laminates 10 and 11 are formed into a predetermined shape and size. A package can be produced by cutting and heat-sealing the second base material 1 having heat-sealability as the inner surface side.
In the case of the packaging material laminate 10 shown in FIG. 1, any one of the two second substrates 1 can be used as the sealant layer. In the case of the packaging material laminate 11 shown in FIG. 2, of the two second base materials 1, the second base material 1 on the side where the other film 5 is not laminated (upper side in FIG. 2) is a sealant. Used as a layer.

  FIG. 3 is an example of a packaging material laminate 20 according to the prior art, and a thermoplastic resin of a type different from the first base material 23 is formed on one surface of the first base material 23 made of a thermoplastic resin film. The second base material 21 that is a film and has heat sealability is a packaging material laminate 20 that is bonded using an adhesive layer 22.

By the way, as each 1st base material 3 which consists of a thermoplastic resin film in each bonding surface 2 of the packaging material laminated body of this invention, for example, a polyamide (PA) resin film and the 2nd which has heat seal property As the substrate 1, for example, there are the following three combinations using an unstretched polyethylene (PE) resin film.
(1): (modified PA) / (air corona treated PE)
(2): (Modified PA) / (Modified PE)
(3): (Air corona-treated PA) / (Modified PE)
Here, the modified PA is a polyamide (PA) resin film having a thickness of 10 to 500 μm in which a heat-adhesive modified layer is formed on at least one surface by surface modification using an atmospheric pressure plasma processing apparatus. It is.
The air corona-treated PA is an air corona-treated polyamide (PA) resin film having a thickness of 10 to 500 μm.
The air corona-treated PE is an unstretched polyethylene (PE) resin film having a heat seal property and having a thickness of 10 to 500 μm and subjected to air corona treatment.
The modified PE is a non-stretched polyethylene (PE) resin film having a heat seal property in which a heat-adhesive modified layer is formed by surface modification using an atmospheric pressure plasma processing apparatus having a thickness of 10 to 500 μm. is there.

In the packaging material laminates 10 and 11 of the present invention, the second base materials 1 and 1 are bonded to both surfaces of the first base material 3 via the bonding surface 2, respectively. For the surface 2, the above three combinations (1) to (3) are possible. Therefore, if the second substrates 1 and 1 on both sides are distinguished (the left side is the front side and the right side is the back side), there are the following nine combinations.
(1/1): (Air corona-treated PE) / (Double-sided modified PA) / (Air corona-treated PE)
(1/2): (Air corona-treated PE) / (Both-side modified PA) / (Modified PE)
(1/3): (air corona treatment PE) / (surface modification treatment / back surface air corona treatment PA) / (modification treatment PE)
(2/1): (modified PE) / (double-sided modified PA) / (air corona-treated PE)
(2/2): (modified PE) / (double-sided modified PA) / (modified PE)
(2/3): (modified PE) / (surface modified / back air corona treated PA) / (modified PE)
(3/1): (modified PE) / (surface air corona treatment / back surface modification PA) / (air corona treatment PE)
(3/2): (modified PE) / (surface air corona treatment / back surface modified PA) / (modified PE)
(3/3): (modified PE) / (double-sided air corona treated PA) / (modified PE)

Here, the double-sided modified PA is a polyamide (PA) resin film having a thickness of 10 to 500 μm, on which a thermal adhesion modified layer is formed by surface modification using an atmospheric pressure plasma processing apparatus on both sides. .
The double-sided air corona-treated PA is a polyamide (PA) resin film having a thickness of 10 to 500 μm and a double-sided air-corona treated.
The surface modification treatment / back surface air corona treatment PA is a polyamide having a thickness of 10 to 500 μm in which a heat adhesion modified layer is formed on the surface by surface modification using an atmospheric pressure plasma treatment apparatus and the back surface is subjected to air corona treatment. PA) resin film.
The surface air corona treatment / back surface modification treatment PA is a polyamide having a thickness of 10 to 500 μm whose surface has been subjected to air corona treatment by forming a thermal adhesion modified layer by surface modification using an atmospheric pressure plasma treatment apparatus. PA) resin film.
When the first base material 3 is a double-sided reforming treatment PA, the two second base materials 1 may be either an air corona treatment PE or a modification treatment PE, respectively.
When the first substrate 3 is a surface modification treatment / back surface air corona treatment PA or a surface air corona treatment / back surface modification treatment PA, the first substrate 3 is bonded to the modified side of the first substrate 3. The second substrate 1 may be either an air corona-treated PE or a modified PE, but the second substrate to be bonded to the air-corona-treated side of the first substrate 3 is a modified PE.
When the first base material 3 is a double-sided air corona treatment PA, the second base material 1 is a modified PE.

  In the case where the second base materials 1 and 1 are simultaneously thermocompression bonded to both surfaces of the first base material 3, the atmospheric pressure plasma treatment or air corona treatment of the surface of the first base material and the back surface of the first base material 3 The atmospheric pressure plasma treatment or air corona treatment may be performed in separate apparatuses and processes. If the first base material has a heat-adhesive modified layer formed on both surfaces by surface modification using an atmospheric pressure plasma processing apparatus, or both surfaces have been subjected to air corona treatment, It is preferable because both sides of the material can be processed under the same processing conditions using one single device or two equivalent devices. At this time, when the first substrate is wound up in a roll shape, it is preferable to change the treatment conditions on both sides as necessary in order to prevent the occurrence of blocking.

In addition, the 1st bonding surface of the 1st base material was made into 1A surface, the other bonding surface was made into 1B surface, and the bonding surface of the 2nd base material bonded to each was distinguished as 2A surface and 2B surface. In this case, the manufacturing method of the present invention can be expressed collectively as follows.
“A second base material, which is a different kind of thermoplastic resin film than the first base material and has heat sealability, is disposed on and bonded to both surfaces of the first base material made of a thermoplastic resin film. A packaging material laminate manufacturing method comprising:
One bonding surface of the first substrate is 1A surface, the other bonding surface is 1B surface, and the bonding surface of the second substrate to be bonded to each is 2A surface, 2B surface,
A thermal adhesion modified layer is formed by surface modification using an atmospheric pressure plasma processing apparatus on one surface of the first substrate 1A surface and the second substrate 2A surface. The other surface is formed with a heat adhesion modified layer by surface modification using an atmospheric pressure plasma processing apparatus or a surface modified layer by air corona treatment, and the 1B surface of the first base material And a thermal adhesive reforming layer is formed by surface modification using an atmospheric pressure plasma processing apparatus on any one of the 2B surfaces of the second base material, and atmospheric pressure is formed on the other surface. Preparing the first base material and the second base material on which a heat-adhesive modified layer by surface modification using a plasma processing apparatus or a surface modified layer by air corona treatment is formed;
The 1A surface and the 2A surface, and the 1B surface and the 2B surface of the first substrate and the second substrate are opposed to each other, and bonded by thermocompression bonding without applying an adhesive and an anchor coating agent. A method for producing a packaging material laminate having less warping and curling. "

Since the packaging material laminates 10 and 11 with less warpage and curl of the present invention have the second base material 1 having heat sealability laminated on one surface, the packaging material laminates 10 and 11 can be suitably used for packaging. . For example, it is possible to obtain a bag body by folding the packaging material laminate 10 with less warping and curling on the inner surface in order to use unstretched polyethylene (PE) as a heat seal layer and heat-sealing the three sides. .
Also, two packaging material laminates 10 and 11 having a small amount of warpage and curl cut to a predetermined size are stacked, heat-sealed at both ends, and further folded into two packaging material laminates 10 and 11 for the bottom. By heat-sealing, a standing pouch-type self-supporting package can be obtained.
Furthermore, a package having various functions such as providing a light-shielding property, providing a resealing chuck, providing a spout, etc., depending on the usage method of the packaging container. A container can be obtained. Specifically, when producing a packaging container having a light shielding property and a barrier property, an aluminum laminate film having a heat sealing property or an easy peel property is separately prepared, and the packaging material lamination with less warping and curling according to the present invention is prepared. The final packaging material laminate can be obtained by pasting with a second base material having heat-sealing properties that is outside the body.
Moreover, the 2nd base material which is a kind of thermoplastic resin film different from the said 1st base material, and has heat-sealing property is arrange | positioned and bonded on both surfaces of the 1st base material which consists of a thermoplastic resin film. In doing so, the second base material is the same kind of thermoplastic resin film, and in the heating step for producing the laminate and the package, a phenomenon occurs in which the second base material melts and adheres to the heating plate or the heating roll side. If so, make a difference in the thickness of the film between the outside and inside of the second substrate disposed on both sides of the first substrate, or make a difference in the type, density or melting point of the thermoplastic resin. The heating process can also be facilitated by using a hot plate.
Further, by increasing the density of the second base material on the opposite surface serving as the seal layer, it is possible to adjust the texture of the laminated body, for example, by increasing the rigidity of the laminated body and raising the waist.

Moreover, the packaging container (bag) used for various uses can be suitably selected from the shape of a well-known packaging container according to the form and property of the content to be filled. For example, a standing pouch shape, a three- or four-side sealed flat bag shape, a gusset bag body, a pillow packaging shape, and a storage case are preferably used.
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. Thus, after the laminate according to the present invention is produced, a cleaner package with reduced amounts of the adhesive and the anchor coat agent using the laminate can be produced.

Here, when laminating the first base material 3 made of a thermoplastic resin film and the second base material 1 having heat sealability, the surface of the resin film using an atmospheric pressure plasma treatment apparatus in advance. Thermoplastic of the same or different type from the first base material 3 and / or the second base material 1 having the heat-sealability, which are formed of the thermoplastic resin film on which a heat-adhesive modified layer is formed by modification. Using a specific film that is a resin film and that has been subjected to air corona treatment, the quality of the surface on which the thermal adhesion modified layer is formed by surface modification by an atmospheric pressure plasma treatment apparatus is determined. That is, the surface of the first base material 3 made of the thermoplastic resin film and / or the surface of the second base material 1 having heat sealability on which the heat-adhesive property-modified layer is formed, and the air corona treatment. Adhesive strength when thermocompression bonding is carried out without facing the air corona treatment surface of a specific film (judgment reference film) and applying an adhesive and an anchor coating agent is JIS K 6854-1 “Adhesive peeling adhesion strength Surface modification using an atmospheric pressure plasma treatment apparatus is required so that the value measured by the measurement method prescribed in “Surface Test Method Part 1: 90 Detachment” is not less than a predetermined value. is there.
The determination reference film is only used for determining the quality of the surface on which the heat-adhesive modified layer is formed by surface modification using an atmospheric pressure plasma processing apparatus. Is not included. For example, when the first base material and / or the second base material is a long film, it is bonded to a judgment reference film in a part of its longitudinal direction, After confirming pass / fail, there is a method in which the first substrate and the second substrate are continuously bonded. In this case, it is preferable to cut (remove) the portion where the laminate is bonded to the determination reference film from the product.
The pass / fail confirmation process by bonding with the judgment reference film does not have to be performed every time when the packaging material laminate is produced, but, for example, the first base material and / or the second base material subjected to the atmospheric pressure plasma treatment. Execute the pass / fail confirmation process as necessary when changing the type of substrate, changing the processing conditions of atmospheric pressure plasma, cleaning the atmospheric pressure plasma processing equipment, replacing parts, etc. Is desirable.
This pass / fail confirmation step is performed both when the surface of the first base material is bonded to the second base material and when the back surface of the first base material is bonded to the second base material. It is preferable.

  In the prior art, by surface modification using an atmospheric pressure plasma processing apparatus, certain functional groups, for example, COOH groups and OH groups can be formed on the film surface, and can be firmly laminated and adhered at low temperatures. However, there is no description that defines a criterion for judging a preferable processing state of the film surface subjected to the atmospheric pressure plasma treatment.

  The inventors of the present invention have disclosed a surface on which a thermoadhesive modified layer of a thermoplastic resin film subjected to atmospheric pressure plasma treatment is formed, and a base material having heat sealability treated with air corona, for example, unstretched polyethylene (PE). It is found that the subtle difference in the state of atmospheric pressure plasma treatment can be confirmed by measuring the adhesive strength of the obtained test laminate by thermocompression bonding with the air corona treatment surface of the resin film, In addition, it is found that a packaging material laminate with less warpage and curl can be obtained by disposing and bonding a base material having heat sealability on both surfaces of a thermoplastic resin film, and the present invention can be achieved. It came.

  In atmospheric pressure plasma processing, the processing conditions such as time for applying plasma to the surface of the film, applied power, frequency, etc., for example, to search for plasma processing conditions for polyamide (PA) resin film, 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” The strength when peeled at a speed of 5 mm / min by the measurement method specified in “Test method Part 1: 90 degree peel” Thus, if the surface modification using the atmospheric pressure plasma processing apparatus is performed so as to be 9.8 N / 25.4 mm or more, a packaging material laminated body with less warpage and curl that can be used for the packaging body is obtained. be able to.

  The surface of the polyethylene terephthalate (PET) resin film subjected to atmospheric pressure plasma treatment on which the heat adhesion modified layer is formed is an air-corona-treated unstretched polyethylene (PE) resin film (unstretched polyethylene film manufactured by Tamapoly Co., Ltd.). Adhesion force when thermocompression bonding is carried out 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 with the air corona treated surface of the product name: SK615P) facing each other. However, the strength when peeled at a speed of 5 mm / min by the measurement method defined in JIS K 6854-1 “Adhesive peel adhesion strength test method Part 1: 90 degree peel” is 5.9 N / 25. If the surface modification using an atmospheric pressure plasma processing apparatus is performed so that it may become 4 mm or more, the curvature which can be used for a package body It can be obtained curl less packaging material laminate.

(Resin film)
The thermoplastic resin film 3 used for the packaging material laminate with less warping and curling of the present invention includes polyethylene terephthalate (PET) resin film, polyamide (PA) resin film, stretched polypropylene (OPP), polyethylene naphthalate (PEN). Examples include resin films, polyacrylonitrile (PAN) resin films, polycarbonate (PC) resin films, polyimide (PI) resin films, polyvinyl chloride (PVC) resin films, and ethylene-vinyl alcohol copolymer (EVOH) resin films. . Examples of the base material 1 having heat sealability include an unstretched polyethylene (PE) resin film, an unstretched polypropylene (CPP) resin film, and a co-extruded film of unstretched polyethylene and unstretched polypropylene (PE / CPP). .
Examples of the thermoplastic resin films 1 and 3 that can be used as a substrate subjected to atmospheric pressure plasma treatment in the present invention include polyethylene terephthalate (PET) resin, polyamide (PA) resin, stretched polypropylene (OPP), and polyvinyl chloride (PVC) resin. , Ethylene-vinyl alcohol copolymer (EVOH), polyethylene naphthalate (PEN) resin, polyacrylonitrile (PAN) resin, polycarbonate (PC) resin, polyimide (PI) resin, unstretched polyethylene (PE) resin, unstretched polypropylene A resin film such as (CPP) resin may be used. The melting points of these thermoplastic resins are polyethylene terephthalate (252 ° C.), polyamide (220 ° C.), stretched polypropylene (164 ° C.), polyvinyl chloride (none), and ethylene-vinyl alcohol copolymer (160 to 190 ° C.), respectively. ), Polyethylene naphthalate (about 270 ° C.), polyacrylonitrile (none), polycarbonate (none), polyimide (none), unstretched polyethylene (105-140 ° C.), unstretched polypropylene (130-165 ° C.), unstretched polyethylene And an unstretched polypropylene coextruded film (PE / CPP) (105 to 165 ° C.). 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.

The heat sealing temperature of the second base material 1 having heat sealability in the case of stacking needs to be performed at a temperature lower than the melting point of the first base material 3 made of a thermoplastic resin film. When thermocompression bonding is performed at a temperature higher than the melting point of the first base material 3 made of a thermoplastic resin film, there is a problem that the resin adheres to the heating roll and the surface of the base material 3 resin becomes rough.
Polyamide (PA) resin film, polyethylene terephthalate (PET) resin film, polyvinyl chloride (PVC) resin film or ethylene-vinyl alcohol copolymer (EVOH) resin film treated with atmospheric pressure plasma, air corona treatment or atmospheric pressure plasma In the heat bonding step when heat-sealing the unstretched polyethylene (PE) resin film or unstretched polypropylene (CPP) resin film whose surface has been modified by the treatment, the thermocompression bonding temperature and pressure are selected. It is preferable. Adhesive strength is improved by increasing the thermocompression bonding temperature, time and pressure. What is necessary is just to select suitably the conditions from which the target adhesive strength is obtained.

The thicknesses of the first base material 3 made of a thermoplastic resin film and the second base material 1 having heat sealability used for the packaging material laminates 10 and 11 with less warpage and curl of the present invention are as follows. The thickness 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, in the method for producing a packaging material laminate with less warpage and curl according to the present invention, when a laminated film is produced by bonding the surface-modified resin films together by thermocompression bonding, the laminated resin film is a roll body. In order to wind up, it is necessary to consider so that the whole thickness may not exceed 500 micrometers.
In addition, when the thickness of the laminated resin film exceeds 500 μm, it is difficult to wind up the laminated resin film on a roll body. It will be produced as a sheet.

(Manufacturing method of packaging material laminate)
In the method for producing the packaging material laminates 10 and 11 with less warpage and curl of the present invention, the first base material 3 made of a thermoplastic resin film and the second base material 1 having heat sealability are bonded together. Lamination can be performed by the following steps (1) to (3).
(1) The surface of the first substrate 3 made of a thermoplastic resin film is subjected to a surface treatment using an atmospheric pressure plasma treatment apparatus to form a heat-adhesive modified layer, or corona in an air atmosphere A surface modified layer is formed by discharge treatment (air corona treatment).
(2) Surface treatment is performed on the surface of the second base material 1 having heat sealing properties using an atmospheric pressure plasma processing apparatus to form a heat-adhesive modified layer, or corona discharge in an air atmosphere A surface modified layer is formed by treatment (air corona treatment). In addition, when the 2nd base material 1 which has heat-sealing property consists of unstretched polypropylene, an atmospheric pressure plasma process is essential.
(3) The surface modified layer of the second base material 1 having heat sealability is formed on the surface of the first base material 3 made of a thermoplastic resin film on which the heat adhesion modified layer is formed. Laminated surfaces are laminated by thermocompression bonding.
However, since either one of the first base material and the second base material has a surface on which a heat-adhesive modified layer is formed by surface modification by an atmospheric pressure plasma processing apparatus, (1) In the case of forming a surface modification layer on the surface of the first base film by corona discharge treatment (air corona treatment) in an air atmosphere, in (2), Surface treatment is performed on the surface using an atmospheric pressure plasma treatment apparatus to form a heat-adhesive modified layer.
Note that 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 packaging material laminates 10 and 11 of the present invention, the two types of resin films to be bonded by thermocompression bonding include a polyethylene terephthalate (PET) resin film, a polyamide ( PA) resin film, stretched polypropylene (OPP) resin film, polyvinyl chloride (PVC) resin film, ethylene-vinyl alcohol copolymer (EVOH) resin film, polyethylene naphthalate (PEN) resin film, polyacrylonitrile (PAN) resin Films, polycarbonate (PC) resin films, polyimide (PI) resin films and the like, and the second base material 1 having heat sealability includes unstretched polyethylene (PE) resin films and unstretched polypropylene (CPP) resin films. , Unstretched A co-extruded film of ethylene and unstretched polypropylene (PE / CPP).

In the packaging material laminates 10 and 11 of the present invention, the second base material 1 is disposed on both surfaces of the first base material 3, and thus at least two sheets are used. The two second substrates 1 and 1 may be films of the same material or different materials.
When any one of the above PE, CPP, and PE / CPP is selected as the second base material 1, 1, one of the second base materials is low density polyethylene (LDPE), and the other is It may be a combination that is recognized as a different material in a lower concept than PE, CPP or PE / CPP, such as linear low density polyethylene (LLDPE).
When two types of the above-mentioned PE, CPP, and PE / CPP are selected as the second base materials 1 and 1, a combination such that one of the second base materials is PE and the other is CPP. Can be considered.

In the present invention, instead of the first substrate 3 made of a single layer film of a thermoplastic resin film, a laminate film in which a thermoplastic resin film is laminated on both sides can be used ((1- 3)). The layer structure is not particularly limited, and examples thereof include PA / adhesive layer / PVC, PA / adhesive layer / PET, and PA / adhesive layer / PA.
When a laminate film in which thermoplastic resin films are laminated on both sides is used as the first base material, the thermoplastic resin films on both sides include PET, PA, OPP, PVC, EVOH, PEN, PAN, PC, PI, etc. Of these, one or two of them are selected. The thermoplastic resin films on both sides may be films of the same material or different materials.

  The other resin film 5 may be a film made of the same material as or different from the first substrate 3 made of a thermoplastic resin film or the second substrate 1 having heat sealability. The other resin film 5 may be a composite film or a laminate film made of a plurality of materials. For example, in the case where an aluminum foil is laminated to provide light shielding properties and barrier properties, and an aluminum laminate film having heat sealing properties or easy peel properties is used as the other resin film 5, the other resin film 5 is "PET / Adhesive layer / metal foil / adhesive layer / easy peel layer ”or“ PA / aluminum deposition film / adhesive layer / PE ”can be employed ((2-2) and (2-5) described later) in the case of). In the other resin film 5, a layer having heat sealability or easy peel property is bonded to the second substrate 1 having heat sealability by thermocompression bonding (heat seal surface 4).

In manufacturing the packaging material laminate 10 with less warpage and curl shown in FIG. 1, when the laminate of the second substrates 1 and 1 on both sides of the first substrate 3 is a thermal laminate, the first substrate 3 It is also possible to laminate one second substrate 1 on one side and then laminate the other second substrate (thermal lamination on each side), or second substrate 1 / first substrate 3 / Lamination can also be performed by thermocompression bonding (three-sided simultaneous thermal lamination) in a state where the three resin films of the second substrate 1 are overlapped.
Since distortion due to heat shrinkage is more even, “simultaneous thermal lamination on both sides” is preferable. The two second substrates 1 and 1 preferably have the same degree of distortion due to heat shrinkage. For example, it is preferable to use films of the same material and the same thickness.

  In the case of thermal lamination of “one-sided thermal lamination”, there is a problem in winding due to the warping or curling of the film immediately after laminating one second substrate 1 on one side of the first substrate 3 In some cases, the unprocessed PET film is also pseudo-bonded to the second substrate 1 as a role of the process paper (that is, the process paper / second base material 1 / first base material). 3) to produce a wound product. Thereby, distortion due to thermal contraction can be suppressed. Further, the second laminate 1 is heat-laminated on the opposite surface of the first substrate 3, and the final laminate ( That is, the second base material 1 / first base material 3 / second base material 1 state) is completed.

In producing the packaging material laminate 11 with less warpage and curl shown in FIG. 2, the packaging material laminate 10 with less warpage and curl is formed by laminating the second substrates 1 and 1 on both surfaces of the first substrate 3. May be laminated with another resin film 5 on the second substrate 1 side. In this case, the other resin film 5 is laminated only on one surface of the packaging material laminate 10, but the packaging material laminate 10 is already a laminate of three or more layers, and the packaging material laminate 10 with less warping and curling is used. Thus, warping and curling are suppressed when laminating with another resin film 5, and as a result, the packaging material laminate 11 with less warping and curling can be obtained.
Moreover, in manufacturing the packaging material laminate 11 with less warpage and curl shown in FIG. 2, after producing a laminate in which the other resin film 5 and the second substrate 1 are laminated on the heat seal surface 4, A laminate composed of “other resin film 5 / heat seal surface 4 / second base material 1”, the first base material 3, and the second base material 1 may be laminated. According to this procedure, the packaging material laminate 11 with less warpage and curl can be obtained in the same manner as the packaging material laminate 10 with less warpage and curl shown in FIG.
When the bonding surface of the other resin film 5 to the second base material 1 has heat sealing properties or easy peel properties, the adhesive and the anchor coating agent are applied even if no surface treatment is applied to the bonding surface. And can be easily bonded to the second substrate 1 by thermocompression bonding. Otherwise, the respective bondings between the other resin film 5 and the second substrate 1 by the same method as the bonding surface 2 of the first substrate 3 and the second substrate 1. The surface can be surface-treated and bonded by thermocompression bonding without applying an adhesive and an anchor coat agent.

The layer configuration of the packaging material laminate with less warpage and curl according to the present invention is not particularly limited, but examples include the following configuration examples. In the following examples, the right side shows the sealant layer.
[Configuration Example of Packaging Material Laminate 10 shown in FIG. 1]
(1-1) PE / bonding surface / PA / bonding surface / PE
(1-2) CPP / bonding surface / PA / bonding surface / CPP
(1-3) PE / bonding surface / PA / adhesive layer / PVC / bonding surface / PE
(1-4) PE / bonding surface / PA / bonding surface / CPP
(1-5) PE / bonding surface / PET / bonding surface / PE
(1-6) CPP / bonding surface / PET / bonding surface / CPP

[Configuration Example of Packaging Material Laminate 11 shown in FIG. 2]
(2-1) PET / adhesive layer / metal foil / adhesive layer / PE / heat seal surface / PE / bonding surface / PA / bonding surface / PE
(2-2) PET / adhesive layer / metal foil / adhesive layer / easy peel layer / heat seal surface / PE / bonding surface / PA / bonding surface / CPP
(2-3) PET / silica vapor deposition film / adhesive layer / PE / heat seal surface / PE / bonding surface / PA / bonding surface / PE
(2-4) PET / silica vapor deposition film / adhesive layer / easy peel layer / heat seal surface / CPP / bonding surface / PA / bonding surface / CPP
(2-5) PA / aluminum deposition film / adhesive layer / PE / heat seal surface / PE / bonding surface / PET / bonding surface / PE
(2-6) PA / aluminum deposition film / adhesive layer / easy peel layer / heat seal surface / CPP / bonding surface / PET / bonding surface / CPP

Moreover, as a structural example of the other laminate film 5 in the packaging material laminated body 11 shown in FIG. 2, the following structural examples are mentioned, for example. In the following example, the side on which the other laminate film 5 is laminated with the second base material 1 through the heat seal surface 4 is shown on the right side.
(3-1) PET / adhesive layer / metal foil / adhesive layer / PE
(3-2) PET / adhesive layer / metal foil / adhesive layer / easy peel layer (3-3) PET / silica vapor deposited film / adhesive layer / PE
(3-4) PET / silica vapor deposition film / adhesive layer / easy peel layer (3-5) PA / aluminum vapor deposition film / adhesive layer / PE
(3-6) PA / aluminum deposition film / adhesive layer / easy peel layer

In the packaging material laminate with less warpage and curl of the present invention, either one of the surface modification treatments for the two types of resin films used for bonding may be performed first as long as it is a stage prior to lamination. Moreover, you may perform the surface modification process simultaneously or in parallel with respect to two types of films to laminate.
Moreover, in this invention, the 2nd base material which is a kind of thermoplastic resin film different from a said 1st base material, and has heat-sealing property is affixed on both surfaces of the 1st base material which consists of a thermoplastic resin film. To combine, a total of three resin films composed of a first base material made of one thermoplastic resin film and two second base materials having heat sealability are overlapped and heated simultaneously. The pressure bonding is preferable in order to obtain a packaging material laminate in which the laminate is less warped and curled.
In addition, the present invention provides a packaging material laminate in which a sealant layer is laminated without using an adhesive and an anchor coating agent, and the laminate is less warped and curled, and a packaging produced using the same. Is.
Therefore, when bonding resin films other than a sealant layer and metal foil, you may use an adhesive agent.

(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. In the surface modification treatment by corona discharge, corona discharge is generated in the atmosphere using a high-frequency power supply voltage, and the electrons and ions generated along with the corona discharge are irradiated to the surface of the resin film, 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 the surface modification treatment is performed on the surface of the resin film using the atmospheric pressure plasma treatment, the corona discharge treatment in a nitrogen gas atmosphere or the large amount in a rare gas atmosphere such as helium or argon. Performed using atmospheric pressure glow plasma treatment.
Further, in the present invention, in the atmospheric pressure plasma treatment, the plasma film generated by the atmospheric pressure plasma treatment apparatus is irradiated for a time and applied to the surface of the resin film so that the heat adhesion modified layer is formed on the film surface. Adjust the power and frequency.

  In the atmospheric pressure plasma processing, the processing conditions such as the time for irradiating the surface of the resin film with the plasma, the applied power, and the frequency are, for example, to search for the plasma processing conditions for polyamide (PA) resin. The surface of the resin film on which the heat-adhesive modified layer is formed is opposed to the air corona-treated surface of an air-corona-treated unstretched polyethylene (PE) resin film (unstretched polyethylene film manufactured by Tamapoly Co., Ltd .; trade name: SK615P). Thus, 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 The strength when peeled at a speed of 5 mm / min by the measurement method specified in “Sheet test method Part 1: 90 degree peel” Can be carried out by examining such that a 9.8 N / 25.4 mm or more, the processing conditions that the surface modification using atmospheric pressure plasma processing apparatus have been made.

  In addition, in order to search for plasma treatment conditions for unstretched polyethylene (PE) resin, the surface of the PE resin film on which the heat-adhesive modified layer is formed, and the air corona-treated polyethylene terephthalate (PET) resin film (Toyobo Co., Ltd. biaxially stretched polyethylene terephthalate film, trade name: E5102) facing the air corona-treated surface, without applying an adhesive and an anchor coating agent, at a temperature of 160 ° C. and a pressure of 0.4 MPa. The adhesive strength when held for 10 seconds and thermocompression bonded is 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 so that the strength at the time of heating is 5.9 N / 25.4 mm or more The made is to have processing conditions can be carried out by the investigation.

The same applies when searching for plasma processing conditions for polyethylene terephthalate (PET) resin, vinyl chloride (PVC) resin, ethylene-vinyl alcohol copolymer (EVOH) resin, and unstretched polypropylene (CPP) resin. The details are as described at the end of the examples.
Also, stretched polypropylene (OPP), co-extruded film of unstretched polyethylene and unstretched polypropylene (PE / CPP), polyethylene naphthalate (PEN) resin, polyacrylonitrile (PAN) resin, polycarbonate (PC) resin, polyimide (PI) When searching for plasma processing conditions for films made of other thermoplastic resins such as resins, the adhesive force is measured by the same method, and the processing conditions using an atmospheric pressure plasma processing apparatus are investigated. be able to.

(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 by thermocompression bonding. Thereby, the adhesive force between the 1st base material and the 2nd base material can be increased.
In addition, even if the bonding process by thermocompression bonding is not the last process of laminated body manufacture, if needed, it is possible to implement the said aging process in the middle of manufacture of a packaging material laminated body with few curvature and curl.

  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, “General Rules for Plastic Films for Food Packaging 7.4 Puncture Strength Test”.
Gelboflex tester test: According to the measurement method defined in MIL-B-131G.
・ 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.
・ Wrapping of the packaging material laminate ・ Measurement of curl: The packaging material laminate is cut into a size of 10 cm × 10 cm, placed on a horizontal table, and the height of the four corners of the packaging material laminate floated from the table. The maximum value was measured. The height distance is preferably measured at all four corners, but if the corner at which the height distance is the maximum value is clear, it is not necessary to measure the height distance at all four corners.
In the present invention, in the warp / curl measurement method, the case where the maximum value of the height distance is 42 mm or less is defined as “packaging material laminate with less warp and curl”. More preferably, the maximum value of the height distance is 25 mm or less.

(Checking the quality of the heat-adhesive modified layer)
In producing a packaging material laminate with less warping and curling according to the present invention, first, various thermoplastic resin films are subjected to surface modification using an atmospheric pressure plasma processing apparatus, and then, thermal adhesive modification is performed. A base material in which the quality of the layer is confirmed is prepared.
Here, using the base material A on which the heat-adhesive modified layer is formed and the base material B, which is a different kind of thermoplastic resin film from the base material A and subjected to air corona treatment, After the surface on which the adhesive property modification layer was formed and the air corona-treated surface of the base material B were opposed to each other and subjected to thermocompression bonding without applying an adhesive and an anchor coating agent, a test laminate was obtained, and then the test The adhesive strength on the bonding surface of the laminate 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 packaging material laminate with less warping and curling according to the present invention, a thermal adhesion modified layer by surface modification was formed in advance using an atmospheric pressure plasma processing apparatus to be used. It is necessary to confirm whether or not the formation state of the heat-adhesive modified layer of the substrate A is appropriate.
In addition, whether the formation state of the heat-adhesive modified layer is appropriate is determined by using a base material B that is a different type of thermoplastic resin film and subjected to air corona treatment. After the surface on which the heat-adhesive modified layer is formed and the air corona-treated surface of the base material B are opposed to each other without applying the adhesive and the anchor coat agent, the test laminate is obtained by thermocompression bonding. It is determined by whether or not the adhesive force on the bonding surface of the test laminate 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 having a thickness of 15 μm (biaxially stretched polyamide film manufactured by Kojin Co., Ltd., trade name: Bonil W), 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. Thus, a heat seal layer laminate of surface modification example 1 was obtained. About the obtained heat-seal layer laminate of surface modification example 1, when the adhesive strength between the bonded films was measured, the measurement result of the peel strength was 22.5 N / 25.4 mm.

(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 heat seal layer laminate of surface modification example 2. The obtained heat-seal layer 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)
An unstretched polyethylene (PE) 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 non-stretched polyethylene (PE) resin film having a thickness of 60 μm (unstretched polyethylene film manufactured by Tamapoly Co., Ltd., trade name: SK615P), a surface modification treatment was performed using an atmospheric pressure plasma treatment apparatus, and surface modification example 3 The surface-modified unstretched polyethylene (PE) resin film was obtained.
Next, the surface of the resin film of surface modification example 3 on which the heat adhesion modified layer was formed, and a commercially available air corona-treated polyethylene terephthalate (PET) resin film (biaxially stretched polyethylene manufactured by Toyobo Co., Ltd.) A surface modification example 3 is made by facing the air corona-treated surface of a terephthalate film, trade name: E5102) and applying the same conditions as in surface modification example 1 without applying an adhesive and an anchor coat agent. A heat seal layer laminate was obtained. The obtained heat-seal layer laminate of Surface Modification Example 3 had a measured peel strength of 8.0 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. An unstretched polyethylene (PE) resin film was obtained. The processing conditions are an irradiation time of 0.005 s, an applied power of 20 W, and a frequency of 13.56 MHz.
Next, using the obtained resin film of surface modification example 4, the same air corona-treated polyethylene terephthalate (PET) resin film as in surface modification example 3 was bonded under the same conditions as in surface modification example 1. And the laminated body of the heat seal layer of the surface modification example 4 was obtained. The obtained heat seal layer laminate of surface modification example 4 had a measured peel strength of 2.5 N / 25.4 mm.

(Example of surface modification by atmospheric pressure plasma treatment 5)
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 having a thickness of 12 μm (biaxially stretched polyethylene terephthalate film manufactured by Toyobo Co., Ltd., trade name: E5200), surface modification is performed using an atmospheric pressure plasma treatment apparatus. The surface-modified polyethylene terephthalate (PET) resin film of Example 5 was obtained.
Next, the surface on which the heat adhesion modified layer of the resin 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 name: 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, heat of surface modification example 5 A laminate of seal layers was obtained. The obtained heat-seal layer laminate of surface modification example 5 had a measured peel strength of 7.9 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 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 the surface modification example 6, it is bonded to a commercially available air-corona-treated unstretched polyethylene (PE) resin film under the same conditions as the surface modification example 5. Thus, a heat seal layer laminate of surface modification example 6 was obtained. The obtained heat-seal layer laminate of surface modification example 6 had a measured peel strength of 3.9 N / 25.4 mm.

(Example of surface modification by atmospheric pressure plasma treatment 7)
A polyvinyl chloride (PVC) resin film was surface-modified using an atmospheric pressure plasma treatment apparatus. The processing conditions are an irradiation time of 0.27 s, an applied power of 2.2 kW, and a frequency of 40 kHz.
Using a polyvinyl chloride (PVC) resin film with a thickness of 19 μm (polyvinyl chloride film manufactured by Asahi Kasei Chemicals Co., Ltd., trade name: Saran-UB), surface modification treatment was performed using an atmospheric pressure plasma treatment apparatus. A surface-modified polyvinyl chloride (PVC) resin film of Example 7 was obtained.
Next, the surface on which the heat adhesion modified layer of the resin film of surface modification example 7 was formed, and a commercially available air-corona-treated unstretched polyethylene (PE) resin film (unstretched polyethylene film manufactured by Tamapoly Co., Ltd.) , Product name: SK615P) facing the air corona-treated surface, without applying an adhesive and an anchor coating agent, holding at a temperature of 140 ° C. and a pressure of 0.4 MPa for 10 seconds, thermocompression bonding, and surface modification A laminate of the heat seal layer of Example 7 was obtained. The obtained heat seal layer laminate of surface modification example 7 had a measured peel strength of 5.6 N / 25.4 mm.

(Example 8 of surface modification by atmospheric pressure plasma treatment)
An ethylene-vinyl alcohol copolymer (EVOH) resin film was surface-modified using an atmospheric pressure plasma treatment apparatus. The processing conditions are an irradiation time of 0.27 s, an applied power of 2.2 kW, and a frequency of 40 kHz.
Using an ethylene-vinyl alcohol copolymer (EVOH) resin film having a thickness of 15 μm (an ethylene-vinyl alcohol copolymer film manufactured by Kuraray Trading Co., Ltd., trade name: EVAL EF-XL) in an atmospheric pressure plasma processing apparatus. Surface modification treatment was performed to obtain a surface-modified ethylene-vinyl alcohol copolymer (EVOH) resin film of surface modification example 8.
Next, the surface on which the heat adhesion modified layer of the resin film of surface modification example 8 was formed and a commercially available air-corona-treated unstretched polyethylene (PE) resin film (unstretched polyethylene film manufactured by Tamapoly Co., Ltd.) , Product name: SK615P) facing the air corona-treated surface, and applying under the same conditions as surface modification example 1 without applying an adhesive and an anchor coat agent, heat of surface modification example 8 A laminate of seal layers was obtained. The obtained heat seal layer laminate of surface modification example 8 had a measured peel strength of 20.1 N / 25.4 mm.

(Example 9 of surface modification by atmospheric pressure plasma treatment)
An unstretched polypropylene (CPP) resin film was surface-modified using an atmospheric pressure plasma treatment apparatus. The processing conditions are an irradiation time of 0.27 s, an applied power of 2.2 kW, and a frequency of 40 kHz.
Using an unstretched polypropylene (CPP) resin film having a thickness of 60 μm (unstretched polypropylene film manufactured by Toyobo Co., Ltd., trade name: Pyrene P1146), surface modification treatment is performed using an atmospheric pressure plasma treatment apparatus. The surface-modified polypropylene (CPP) resin film of Example 9 was obtained.
Next, the surface of the resin film of surface modification example 9 on which the heat adhesion modified layer was formed and a commercially available 12 μm polyethylene terephthalate (PET) resin film treated with air corona (biaxially manufactured by Toyobo Co., Ltd.) Stretched polyethylene terephthalate film, trade name: E5102) facing the air corona-treated surface, without applying an adhesive or anchor coating agent, held at a temperature of 190 ° C and a pressure of 0.4 MPa for 10 seconds and thermocompression bonded Thus, a heat seal layer laminate of surface modification example 9 was obtained. The obtained heat-seal layer laminate of surface modification example 9 had a measured peel strength of 16.4 N / 25.4 mm.

(Example 10 of surface modification by atmospheric pressure plasma treatment)
The surface modification of the surface modification example 10 was performed by performing the same operation as the surface modification example 9 except that the atmospheric pressure plasma irradiation time, applied power, and frequency were changed in the weak direction in the atmospheric pressure plasma processing apparatus. An unstretched polypropylene (CPP) resin film was obtained. The processing conditions are an irradiation time of 0.12 s, an applied power of 1.0 kW, and a frequency of 20 kHz.
Next, using the obtained resin film of the surface modification example 10 and pasting with a commercially available polyethylene terephthalate (PET) resin film treated with an air corona under the same conditions as the surface modification example 9, A heat seal layer laminate of surface modification example 10 was obtained. The obtained heat-seal layer laminate of surface modification example 10 had a measured peel strength of 0.2 N / 25.4 mm.

As described above, surface-modified resin films of surface modification examples 1 to 10 were obtained using an atmospheric pressure plasma processing apparatus. The heat-adhesive modified layer of the obtained surface modification examples 1 to 10 and an air corona-treated resin film were bonded together by thermocompression bonding, and the heat seal layer laminate of the surface modification examples 1 to 10 was laminated. Obtained.
Table 1 shows the results of measuring the peel strength of the obtained heat-seal layer laminates of surface modification examples 1 to 10.

Next, using the surface-modified resin films of the obtained surface modification examples 1, 2, 3, 5, 6, 9, 10 and commercially available air corona-treated thermoplastic resin films The packaging material laminates of Examples 1 to 4 and Comparative Examples 1 to 3 were produced by bonding only by thermocompression bonding without using an adhesive or an anchor coat agent.
Moreover, in order to compare with the packaging material laminated body produced by this invention, it bonded by the dry lamination system using the adhesive agent which is a prior art, and produced the packaging material 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 (manufactured by Tamapoly Co., Ltd.) An air-corona-treated surface of an unstretched polyethylene film, trade name: SK615P) is thermocompression bonded with a heating roll at a speed of 5 m / min, a temperature of 150 ° C., and a pressure of 0.23 MPa without applying an adhesive and an anchor coating agent. Then, the packaging material laminate of Example 1 was obtained. Furthermore, using the obtained packaging material laminate of Example 1, a packaging container of a standing pouch type and a four-side seal bag was prepared, and various tests relating to the packaging container were then performed.

(Comparative Example 1)
In the surface modification example 2 above, a surface on which a heat-adhesive modified layer of a polyamide (PA) resin film is formed, and an air corona-treated surface of a commercially available air-corona-treated unstretched polyethylene (PE) resin film, The packaging material laminated body of the comparative example 1 was obtained like Example 1 except having used the laminated body by which was bonded. Furthermore, using the obtained packaging material laminate of Comparative Example 1, a packaging container of a standing pouch type and a four-side seal bag was produced, and various tests relating to the packaging container were then performed.

(Example 2)
The surface of the surface modification example 5 in which a heat-adhesive modified layer of a polyethylene terephthalate (PET) resin film is formed, and an unstretched polyethylene (PE) resin film subjected to air corona treatment (unstretched polyethylene manufactured by Tamapoly Co., Ltd. A packaging material laminate of Example 2 was obtained in the same manner as in Example 1 except that a laminate on which the air corona-treated surface of a film and a trade name: SK615P) was bonded was used. Furthermore, after producing the packaging container of a four-side seal bag using the obtained packaging material laminated body of Example 2, various tests regarding the packaging container were performed.

(Comparative Example 2)
The surface of the surface modification example 6 in which the heat-adhesive modified layer of the polyethylene terephthalate (PET) resin film is formed and the air corona-treated surface of the air-corona-treated unstretched polyethylene (PE) resin film are bonded together. A packaging material laminate of Comparative Example 2 was obtained in the same manner as in Example 1 except that the laminate was used. Furthermore, after producing the packaging container of a four-side seal bag using the packaging material laminated body of the obtained comparative example 2, the various tests regarding a packaging container were done.

(Example 3)
The surface of the surface modification example 9 on which the heat adhesion modified layer of the unstretched polypropylene (CPP) resin film is formed, and the air-corona-treated polyamide (PA) resin film (biaxially stretched polyamide manufactured by Unitika Ltd.) Film, trade name: Emblem ONMB) The air corona-treated surface of the film is thermocompression bonded with a heating roll at a speed of 5 m / min, a temperature of 185 ° C., and a pressure of 0.23 MPa without applying an adhesive and an anchor coating agent. To obtain a packaging material laminate of Example 3. Furthermore, after producing the packaging container of a four-side seal bag using the obtained packaging material laminated body of Example 3, various tests regarding the packaging container were performed.

(Comparative Example 3)
In the surface modification example 10 above, the surface of the unstretched polypropylene (CPP) resin film on which the heat adhesion modified layer was formed and the air corona-treated surface of the air-corona-treated polyamide (PA) resin film were bonded together. A packaging material laminate of Comparative Example 3 was obtained in the same manner as in Example 3 except that the laminate was used. Furthermore, after producing the packaging container of a four-side seal bag using the obtained packaging material laminated body of the comparative example 3, the various tests regarding a packaging container were done.

Example 4
The surface of the surface modification example 1 of the polyamide (PA) resin film on which the heat adhesion modified layer is formed, and the heat of the surface-modified surface modification example 3 of the unstretched polyethylene (PE) resin film The surface on which the adhesive reforming layer was formed was bonded, and heat lamination was performed under the same conditions as in Example 1 to obtain a packaging material laminate of Example 4. Furthermore, using the obtained packaging material laminate of Example 4, a packaging container of a standing pouch type and a four-side seal bag was prepared, and various tests relating to the packaging container were then performed.

(Comparative Example 4)
According to the prior art, an air corona-treated surface of a polyamide (PA) resin film (biaxially stretched polyamide film manufactured by Kojin Co., Ltd .; trade name: Bonil RX) having a thickness of 15 μm and a commercially available air corona-treated unstretched polyethylene ( PE) A resin film (Tamapoly Co., Ltd. unstretched polyethylene film, trade name: SK615P) facing the air corona-treated surface, and after applying an adhesive, it was pressure-bonded with a pressure roll, subjected to aging and subjected to aging. A packaging material laminate was obtained. Furthermore, using the obtained packaging material laminate of Comparative Example 4, a packaging container of a standing pouch type and a four-side seal bag was prepared, and various tests relating to the packaging container were then performed.

Using the laminates of Examples 1 to 4 and Comparative Examples 1 to 4 obtained as described above, a packaging container of a standing type or a four-side seal bag was produced, and various tests relating to the packaging container were performed. The test results obtained are shown in Table 3.
Table 2 is a table summarizing the layer configurations of the packaging material laminates of Examples 1 to 4 and Comparative Examples 1 to 4 that are packaging material laminates with less warpage and curl according to the present invention.

Table 3 shows a standing type or four-side seal bag package (packaging) produced using the packaging material laminates of Examples 1 to 4 and Comparative Examples 1 to 4 which are packaging material laminates with less warpage and curl according to the present invention. It is the result of the various tests done about the container.
Comparative Example 4 is a test result of a package (packaging container) produced using a packaging material laminate produced by a dry lamination method using an adhesive according to the prior art.
Examples 1 to 4 are test results of a package (packaging container) produced using a packaging material laminate in which a laminate of heat seal layers was produced by thermocompression bonding according to the present invention. Even if the test results of Comparative Example 4 which is a package (packaging container) produced using a packaging material laminate according to the prior art and the test results of Examples 1 to 4 which are packages according to the present invention are compared, There is no significant difference.
Therefore, the packaging material laminated body with less warpage and curl according to the present invention has the same level of properties as the packaging material laminated body by the dry laminating method using the adhesive according to the prior art, and the packaging body (packaging container) It can be used as a constituent material without causing any problems.

  Table 4 shows the results of measuring the warpage and curl of the laminate of the packaging material laminate of Comparative Example 4 produced by the prior art and the packaging material laminate of Example 1 according to the present invention. The packaging material laminate of Example 1 is a packaging material laminate with less warping and curling than a packaging material laminate produced by a dry lamination method using an ordinary conventional adhesive.

Table 5 shows the 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 heat-seal layer of a laminated body after the storage period between.
In the packaging container of Example 1, the occurrence of the delamination (peeling from the bonding surface) phenomenon did not occur, and the packaging produced using a laminate produced by a dry laminating method using an adhesive according to a conventional conventional technique It has the same durability as the container.

Table 6 shows a process of bonding a heat seal layer, which is the innermost layer of the packaging body, of Comparative Example 4, which is a packaging container produced using a laminate produced by a dry lamination method using an adhesive according to the prior art. The solvent amount (kg) required when processing 1,000 m with a substrate width of 1,000 mm by the dry laminating method is calculated.
The amount of solvent required for dry lamination was 38.7 (kg). On the other hand, in the case of the present invention, since no adhesive is used to bond the heat seal layer that is the innermost layer of the package, the residual solvent of the heat seal layer can be reduced, and contamination to the contents can be reduced. Prevent, and lead to suppressing the adverse effect on the ingredients.

  Moreover, when the test results of Table 1 and Table 3 are comprehensively judged, the adhesive force of the heat-adhesive modified layer by surface modification applied to the thermoplastic resin film using an atmospheric pressure plasma processing apparatus is as follows. It is sufficient to control appropriately. If it does so, the resin film in which the heat-adhesive property modification layer by the surface modification of the atmospheric pressure plasma process suitable for implementing this invention was formed can be obtained.

(Plasma treatment for polyamide resin)
In order to determine the quality of the surface on which the thermal adhesion modified layer is formed by surface modification with an atmospheric pressure plasma processing apparatus with respect to the polyamide (PA) resin film, select a specific film as a determination criterion, A reference value is set that ensures that the adhesive strength when the laminate is obtained is the required strength. Then, when the adhesive strength when thermocompression bonding is equal to or higher than the reference value without applying the adhesive and the anchor coat agent, the determination of the surface on which the thermoadhesive modified layer is formed is good. Specifically, the surface on which the heat-adhesive modified layer is formed by surface modification of a polyamide (PA) resin film, and as a judgment reference film, for example, a commercially available air-corona-treated unstretched polyethylene (PE) resin The film (unstretched polyethylene film manufactured by Tamapoly Co., Ltd., trade name: SK615P) is opposed to the air corona-treated surface and is kept 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 adhesive strength when thermocompression bonding was performed was 9.8 N / 25 as measured by the measurement method specified in JIS K 6854-1, “Adhesive Peeling Adhesive Strength Test Method Part 1: 90 ° Peeling”. The surface may be modified using an atmospheric pressure plasma processing apparatus so that the thickness is 4 mm or more.

(Plasma treatment for unstretched polyethylene resin)
In order to determine the quality of the surface on which the heat-adhesive modified layer is formed by surface modification with an atmospheric pressure plasma processing apparatus with respect to the unstretched polyethylene (PE) resin film, A surface on which a heat-adhesive modified layer is formed by surface modification and an air corona of a commercially available air corona-treated polyethylene terephthalate (PET) resin film (biaxially stretched polyethylene terephthalate film manufactured by Toyobo Co., Ltd., trade name: E5102) The adhesive strength when heated and pressure-bonded 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 opposite to the treated surface is JIS K 6854-1 “ The value measured by the measuring method specified in “Adhesive Peeling Bond Strength Test Method Part 1: 90 degree peeling” is 5.9 N / 2 What is necessary is just to perform the surface modification using an atmospheric pressure plasma processing apparatus so that it may become 5.4 mm or more.

(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 depending on the quality, and 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) 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 The strength measured by the measurement method specified in “Strength Test Method Part 1: 90 degree Peeling” is 5.9 N / 25. What is necessary is just to carry out the surface modification using an atmospheric pressure plasma processing apparatus so that it may become 4 mm or more.

(Plasma treatment for polyvinyl chloride resin)
In order to judge the quality of the surface on which the thermal adhesion modified layer is formed by surface modification with an atmospheric pressure plasma processing apparatus with respect to the polyvinyl chloride (PVC) resin film, the polyvinyl chloride (PVC) resin film Surface with heat-adhesive modified layer formed by surface modification and air corona treated surface of commercially available air-corona-treated unstretched polyethylene (PE) resin film (unstretched polyethylene film, trade name: SK615P manufactured by Tamapoly Co., Ltd.) Adhesive strength when heated and pressure-bonded by holding at a temperature of 140 ° 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” In order that the value measured by the measurement method defined in “Peeling adhesive strength test method Part 1: 90 degree peeling” is 3.9 N / 25.4 mm or more, Surface modification using an atmospheric pressure plasma processing apparatus may be performed.

(Plasma treatment for ethylene-vinyl alcohol copolymer resin)
In order to determine the quality of the surface on which the heat adhesion modified layer was formed by surface modification with an atmospheric pressure plasma treatment apparatus on an ethylene-vinyl alcohol copolymer (EVOH) resin film, A surface on which a heat-adhesive modified layer is formed by surface modification of a polymer (EVOH) resin film, and a commercially available air-corona-treated unstretched polyethylene (PE) resin film (unstretched polyethylene film, product manufactured by Tamapoly Co., Ltd.) Name: SK615P) facing the air corona treatment surface, without applying an adhesive and an anchor coat agent, the adhesive strength when heated and pressed for 10 seconds at a temperature of 160 ° C. and a pressure of 0.4 MPa, Measured 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 may be performed so that the value becomes 5.9 N / 25.4 mm or more.

(Plasma treatment for unstretched polypropylene resin)
In order to determine the quality of the surface on which the heat adhesion modified layer is formed by surface modification with an atmospheric pressure plasma processing apparatus with respect to the unstretched polypropylene (CPP) resin film, the unstretched polypropylene (CPP) resin film A surface on which a heat-adhesive modified layer is formed by surface modification and an air corona of a commercially available air corona-treated polyethylene terephthalate (PET) resin film (biaxially stretched polyethylene terephthalate film manufactured by Toyobo Co., Ltd., trade name: E5102) The adhesive strength when heated and pressure-bonded by holding at a temperature of 190 ° C. and a pressure of 0.4 MPa for 10 seconds without applying an adhesive and an anchor coating agent opposite to the treated surface is JIS K 6854-1 “ The value measured by the measuring method defined in “Adhesive Peeling Bond Strength Test Method Part 1: 90 degree peeling” is 5. What is necessary is just to carry out the surface modification | reformation using an atmospheric pressure plasma processing apparatus so that it may become 9N / 25.4mm or more.

In the pass / fail confirmation method using the judgment reference film, a base material having a surface on which a heat adhesion modified layer is formed when the 1A surface of the first base material is bonded to the 2A surface of the second base material. When the material is different from the material of the substrate having the surface on which the heat-adhesive modified layer is formed when the 1B surface of the first substrate is bonded to the 2B surface of the second substrate, It is preferable to independently select the criteria film according to (1) and (2).
(1) When laminating the 1A surface of the first substrate and the 2A surface of the second substrate, a substrate on which a heat-adhesive modified layer is formed between the both substrates, and a criterion film Choose the right combination.
(2) When laminating the 1B surface of the first base material and the 2B surface of the second base material, a base material on which a heat-adhesive modified layer is formed between the two base materials, and a judgment reference film Choose the right combination.

  When the first substrate is made of a laminate film, the thermoplastic resin film having the 1A surface of the first substrate and the thermoplastic resin film having the 1B surface of the first substrate are made of different materials. It may be a film. Also in that case, it is preferable to independently select the judgment reference film according to the above (1) and (2).

Needless to say, the same judgment reference film may be used when it is allowed to use the same kind of judgment reference film as a result of selecting the judgment reference film independently according to the above (1) and (2).
In the above (1) and (2), the appropriate combination of the base material on which the heat adhesion modified layer is formed and the judgment reference film is the same combination, and the heat adhesion modified layer is formed. The base material modification processing conditions are the same (for example, when the first base material 1A and 1B surfaces are reformed under the same conditions, or the second base material 2A and 2B surfaces are the same) When the modification treatment is performed under the conditions), it is possible to confirm the quality of both surfaces by bonding the base material on which the heat-adhesive modified layer is formed and the determination reference film only once.

According to the present invention, an atmospheric pressure plasma-treated resin film necessary for obtaining a laminate bonded by thermocompression bonding to a thermoplastic resin film without using an adhesive and an anchor coating agent. By determining whether or not the formation state of the heat-adhesive modified layer is good, it is possible to effectively perform the atmospheric pressure plasma treatment.
In addition, according to the present invention, a laminate manufacturing method, a laminate, and a packaging container produced using the laminate, which are bonded without using an adhesive and an anchor coating agent, and have less warpage and curl of the laminate. 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, packaging containers prepared using the laminate according to the present invention are 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.
In addition, according to the present invention, a laminate and its use can be used without attaching an adhesive and an anchor coat agent, that is, without using any organic solvent, to bond the heat seal layer that is the innermost layer of the package. Therefore, it is possible to reduce the residual solvent in the heat seal layer, prevent contamination to the contents, and suppress adverse effects on the components.

DESCRIPTION OF SYMBOLS 1,21 ... Base material which has heat-sealing property, 2 ... Bonding surface, 3,23 ... Thermoplastic resin film, 22 ... Adhesive layer, 4 ... Heat-sealing surface, 5 ... Other laminate films, 10, 11 ... Packaging material laminate with less warpage and curl of the present invention, 20... Packaging material laminate according to the prior art.

Claims (15)

A second base material, which is a different kind of thermoplastic resin film from the first base material and has heat sealability, is disposed on and bonded to both surfaces of the first base material made of a thermoplastic resin film. A packaging material laminate manufacturing method comprising:
One bonding surface of the first substrate is 1A surface, the other bonding surface is 1B surface, and the bonding surface of the second substrate to be bonded to each is 2A surface, 2B surface,
Both the 1A surface and 1B surface, which are the bonding surfaces of the first base material, are provided with a thermal adhesion modified layer by surface modification using an atmospheric pressure plasma processing apparatus, and the second base material. On the 2A and 2B surfaces, which are the bonding surfaces, a thermal adhesion modified layer is formed by surface modification using an atmospheric pressure plasma processing apparatus, or a surface modified layer is formed by air corona treatment. Preparing the first base material and the second base material,
The 1A surface and the 2A surface, and the 1B surface and the 2B surface of the first substrate and the second substrate are opposed to each other, and bonded by thermocompression bonding without applying an adhesive and an anchor coating agent. A method for producing a packaging material laminate having less warping and curling. A second base material, which is a different kind of thermoplastic resin film from the first base material and has heat sealability, is disposed on and bonded to both surfaces of the first base material made of a thermoplastic resin film. A packaging material laminate manufacturing method comprising:
One bonding surface of the first substrate is 1A surface, the other bonding surface is 1B surface, and the bonding surface of the second substrate to be bonded to each is 2A surface, 2B surface,
A thermal adhesive modified layer is formed by surface modification using an atmospheric pressure plasma processing apparatus on either one of the 1A surface and 1B surface, which are the bonding surfaces of the first base material, A surface modification layer formed by air corona treatment is formed on the surface, and the bonding surface of the second substrate is bonded to the bonding surface on which the heat adhesion modified layer of the first substrate is formed. The surface modification layer is formed by air corona treatment, or the heat adhesion modification layer is formed by surface modification using an atmospheric pressure plasma treatment apparatus, and the surface modification layer of the first base material is formed. On the bonding surface of the second substrate to be bonded to the bonding surface on which is formed, a heat adhesion modified layer is formed by surface modification using an atmospheric pressure plasma processing apparatus. Preparing the base material and the second base material,
The 1A surface and the 2A surface, and the 1B surface and the 2B surface of the first substrate and the second substrate are opposed to each other, and bonded by thermocompression bonding without applying an adhesive and an anchor coating agent. A method for producing a packaging material laminate having less warping and curling. A second base material, which is a different kind of thermoplastic resin film from the first base material and has heat sealability, is disposed on and bonded to both surfaces of the first base material made of a thermoplastic resin film. A packaging material laminate manufacturing method comprising:
One bonding surface of the first substrate is 1A surface, the other bonding surface is 1B surface, and the bonding surface of the second substrate to be bonded to each is 2A surface, 2B surface,
A surface modified layer by air corona treatment is formed on both the 1A surface and 1B surface, which are the bonding surfaces of the first substrate, and the 2A surface and 2B surface, which are the bonding surfaces of the second substrate. For both, the first base material and the second base material in which a heat-adhesive modified layer is formed by surface modification using an atmospheric pressure plasma processing apparatus are prepared,
The 1A surface and the 2A surface, and the 1B surface and the 2B surface of the first substrate and the second substrate are opposed to each other, and bonded by thermocompression bonding without applying an adhesive and an anchor coating agent. A method for producing a packaging material laminate having less warping and curling.   In pasting the first base material and the second base material, the thermal adhesion modified layer is formed in advance by surface modification of the resin film using an atmospheric pressure plasma processing apparatus. Using the second base material and / or the first base material, and the same or different kind of thermoplastic resin film, and a judgment standard film for atmospheric pressure plasma treatment effect obtained by air corona treatment, Applying an adhesive and an anchor coating agent so that the surface of the base material of 2 and / or the surface of the first base material on which the heat adhesion modified layer is formed and the air corona treatment surface of the judgment reference film face each other. After obtaining the test laminate by thermocompression, the adhesive strength on the bonding surface of the test laminate is measured, and the second substrate and / or the first substrate is improved in thermal adhesion. 2. The quality of the layer formation state is confirmed. Any method for producing a warp or curl less packaging material laminate according to the 3. When the base material on which the heat-adhesive modified layer is formed using an atmospheric pressure plasma processing apparatus is a polyamide (PA) resin film, an air-corona-treated unstretched polyethylene (PE) resin film as the determination reference film The adhesive strength when heated and pressed by holding for 10 seconds at a temperature of 160 ° C. and a pressure of 0.4 MPa is JIS K 6854-1 “Adhesive Peeling Adhesive Strength Test Method Part 1: 90 degree peeling” Confirmed that the value measured by the measurement method specified in the above is 9.8 N / 25.4 mm or more,
When the base material on which the heat-adhesive modified layer is formed using an atmospheric pressure plasma processing apparatus is an unstretched polyethylene (PE) resin film, an air corona-treated polyethylene terephthalate (PET) resin as the determination reference film Using a film, 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 is JIS K 6854-1 “Adhesive Peeling Adhesive Strength Test Method Part 1: 90 degree peeling. Confirmed that the value measured by the measurement method stipulated in "" is 5.9N / 25.4mm or more,
When the base material on which the heat-adhesive modified layer is formed using an atmospheric pressure plasma treatment apparatus is a polyethylene terephthalate (PET) resin film, an unstretched polyethylene (PE) resin treated with air corona as the determination reference film Using a film, 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 is JIS K 6854-1 “Adhesive Peeling Adhesive Strength Test Method Part 1: 90 degree peeling. Confirmed that the value measured by the measurement method stipulated in "" is 5.9N / 25.4mm or more,
When the base material on which the heat-adhesive modified layer is formed using an atmospheric pressure plasma processing apparatus is a polyvinyl chloride (PVC) resin film, uncorrelated polyethylene (PE) that has been subjected to air corona treatment as the determination reference film Adhesive strength when a resin film is used and held for 10 seconds at a temperature of 140 ° C. and a pressure of 0.4 MPa is JIS K 6854-1 “Adhesive Peeling Bond Strength Test Method Part 1: 90 ° Confirm that the value measured by the measurement method specified in “peeling” is 3.9 N / 25.4 mm or more,
When the base material on which the heat-adhesive modified layer is formed using an atmospheric pressure plasma processing apparatus is an ethylene-vinyl alcohol copolymer (EVOH) resin film, an air-corona-treated unstretched film as the determination reference film Adhesive strength when a polyethylene (PE) resin film is used for 10 seconds by holding at a temperature of 160 ° C. and a pressure of 0.4 MPa for 10 seconds is JIS K 6854-1 “Adhesive peel adhesion strength test method 1 Part: 90 degree peeling ”, and confirm that the value measured by the measuring method is 5.9 N / 25.4 mm or more,
When the base material on which the heat adhesion modified layer is formed using an atmospheric pressure plasma treatment apparatus is an unstretched polypropylene (CPP) resin film, an air corona-treated polyethylene terephthalate (PET) resin as the determination reference film Using a film, the adhesive strength when heated and pressure-bonded by holding at a temperature of 190 ° C. and a pressure of 0.4 MPa for 10 seconds is JIS K 6854-1 “Adhesive Peeling Adhesive Strength Test Method Part 1: 90 degree peeling 5. The method for producing a packaging material laminate with less warpage and curl according to claim 4, wherein a value measured by the measurement method defined in “4” is confirmed to be 5.9 N / 25.4 mm or more.   The first base material is polyethylene terephthalate (PET), polyamide (PA), expanded polypropylene (OPP), polyethylene naphthalate (PEN), polyacrylonitrile (PAN), polycarbonate (PC), polyimide (PI), polychlorinated. One type selected from the group consisting of vinyl (PVC) and ethylene-vinyl alcohol copolymer (EVOH), and the second base material is unstretched polyethylene (PE), unstretched polypropylene (CPP) The warpage according to any one of claims 1 to 5, wherein the warpage is one or two selected from the group consisting of a coextruded film (PE / CPP) of unstretched polyethylene and unstretched polypropylene. Manufacturing method for packaging material laminate with less curl.   The first substrate is a laminate film in which a thermoplastic resin film is laminated on both sides, and the thermoplastic resin film on both sides of the first substrate is made of polyethylene terephthalate (PET), polyamide (PA), stretched Among the group consisting of polypropylene (OPP), polyethylene naphthalate (PEN), polyacrylonitrile (PAN), polycarbonate (PC), polyimide (PI), polyvinyl chloride (PVC), and ethylene-vinyl alcohol copolymer (EVOH) 1 type or 2 types selected from the above, and the second substrate is unstretched polyethylene (PE), unstretched polypropylene (CPP), co-extruded film of unstretched polyethylene and unstretched polypropylene (PE / CPP) It is one or two types selected from the group consisting of Method for producing a warp or curl less packaging material laminate according to any one of claims 1 to 5,.   A packaging material laminate with less warpage and curl, wherein the packaging material laminate is produced by the method for producing a packaging material laminate with less warpage and curl according to any one of claims 1 to 7.   Using the packaging material laminate with less warpage and curl according to claim 8, it is manufactured such that any one of the heat-sealing second base materials is on the inner surface side as a sealant layer. Characteristic packaging. A second base material having a heat sealing property, which is a different kind of thermoplastic resin film from the first base material, is bonded to both surfaces of the first base material made of a thermoplastic resin film,
One bonding surface of the first substrate is a 1A surface, the other bonding surface is a 1B surface, and a bonding surface of the second substrate to be bonded to each is a 2A surface and a 2B surface. ,
Both the 1A surface and 1B surface, which are the bonding surfaces of the first base material, are provided with a thermal adhesion modified layer by surface modification using an atmospheric pressure plasma processing apparatus, and the second base material. On the 2A and 2B surfaces, which are the bonding surfaces, a thermal adhesion modified layer is formed by surface modification using an atmospheric pressure plasma processing apparatus, or a surface modified layer is formed by air corona treatment And
The 1A surface and 2A surface, and the 1B surface and 2B surface of the first base material and the second base material face each other, and are bonded by thermocompression bonding without applying an adhesive and an anchor coat agent. A packaging material laminate with less warping and curling, characterized by being made. A second base material having a heat sealing property, which is a different kind of thermoplastic resin film from the first base material, is bonded to both surfaces of the first base material made of a thermoplastic resin film,
One bonding surface of the first substrate is a 1A surface, the other bonding surface is a 1B surface, and a bonding surface of the second substrate to be bonded to each is a 2A surface and a 2B surface. ,
A thermal adhesive modified layer is formed by surface modification using an atmospheric pressure plasma processing apparatus on either one of the 1A surface and 1B surface, which are the bonding surfaces of the first base material, On the surface, a surface modification layer by air corona treatment is formed, and on the bonding surface of the second substrate to be bonded to the bonding surface on which the heat adhesion modified layer of the first substrate is formed A surface modified layer is formed by air corona treatment, or a thermal adhesion modified layer is formed by surface modification using an atmospheric pressure plasma processing apparatus, and the surface modified layer of the first substrate is formed. On the bonding surface of the second base material to be bonded to the bonded surface, a thermal adhesion modified layer is formed by surface modification using an atmospheric pressure plasma processing apparatus,
The 1A surface and 2A surface, and the 1B surface and 2B surface of the first base material and the second base material face each other, and are bonded by thermocompression bonding without applying an adhesive and an anchor coat agent. A packaging material laminate with less warping and curling, characterized by being made. A second base material having a heat sealing property, which is a different kind of thermoplastic resin film from the first base material, is bonded to both surfaces of the first base material made of a thermoplastic resin film,
One bonding surface of the first substrate is a 1A surface, the other bonding surface is a 1B surface, and a bonding surface of the second substrate to be bonded to each is a 2A surface and a 2B surface. ,
A surface modified layer by air corona treatment is formed on both the 1A surface and 1B surface, which are the bonding surfaces of the first substrate, and the 2A surface and 2B surface, which are the bonding surfaces of the second substrate. In both cases, a thermal adhesion modified layer is formed by surface modification using an atmospheric pressure plasma processing apparatus,
The 1A surface and 2A surface, and the 1B surface and 2B surface of the first base material and the second base material face each other, and are bonded by thermocompression bonding without applying an adhesive and an anchor coat agent. A packaging material laminate with less warping and curling, characterized by being made.   The first base material is polyethylene terephthalate (PET), polyamide (PA), expanded polypropylene (OPP), polyethylene naphthalate (PEN), polyacrylonitrile (PAN), polycarbonate (PC), polyimide (PI), polychlorinated. One type selected from the group consisting of vinyl (PVC) and ethylene-vinyl alcohol copolymer (EVOH), and the second base material is unstretched polyethylene (PE), unstretched polypropylene (CPP) The warpage according to any one of claims 10 to 12, wherein the warpage is one or two selected from the group consisting of a coextruded film (PE / CPP) of unstretched polyethylene and unstretched polypropylene. Packaging material laminate with less curl and curl.   The first substrate is a laminate film in which a thermoplastic resin film is laminated on both sides, and the thermoplastic resin film on both sides of the first substrate is made of polyethylene terephthalate (PET), polyamide (PA), stretched Among the group consisting of polypropylene (OPP), polyethylene naphthalate (PEN), polyacrylonitrile (PAN), polycarbonate (PC), polyimide (PI), polyvinyl chloride (PVC), and ethylene-vinyl alcohol copolymer (EVOH) 1 type or 2 types selected from the above, and the second substrate is unstretched polyethylene (PE), unstretched polypropylene (CPP), co-extruded film of unstretched polyethylene and unstretched polypropylene (PE / CPP) It is one or two types selected from the group consisting of Warping and curling less packaging material laminate according to any of claims 10 to 12 to.   Using the packaging material laminate with less warpage and curl according to any one of claims 10 to 14, manufactured so that one of the second base materials having heat sealability is an inner surface side as a sealant layer. The package characterized by being made.

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