JP2011104821A - Method for producing packaging material laminate, packaging material laminate and package using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a packaging material laminate in which a sealant layer is laminated without using an adhesive and an anchor coat agent and to provide a packaging material laminate and a package produced by using the laminate. <P>SOLUTION: The packaging material laminate comprises: at least one gas barrier layer chosen from a group composed of a metal foil, a vapor deposition film of a metal or a metal oxide and a resin composition layer having a gas barrier property; and a base material having heat sealability. In the method for producing the packaging material laminate, the packaging material laminate 10 is made by laminating a first base material 1 having one exposed surface and an adjoining second base material 3 formed of a thermoplastic resin film by using no adhesive and no anchor coat agent. At either one between an adhesion surface 2 of the first base material 1 and an adhesion surface 2 of the second base material 3, a heat adhesive modified layer is formed by surface modification using an atmospheric pressure plasma treatment apparatus and at another between them, a surface modification layer subjected to air corona treatment or the heat adhesive modified layer is formed. <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. Furthermore, in detail, various liquid forms such as boil and retort food, liquid detergent, liquid bleach, liquid wax, hair care products (including shampoos, rinses, conditioners, etc.), chemicals, liquid cosmetics, etc. For manufacturing packaging material laminates in which sealant layers are laminated without using adhesives and anchor coating agents, packaging material laminates, and the use thereof It is related with the packaging body produced in this way.

Conventionally, packaging for storing, transporting and supplying boiled and retort foods, hair care products, household products, etc., is flexible packaging with a synthetic resin film having a sealant layer on the inner surface and heat-sealed. Bags and packaging containers (hereinafter referred to as packaging) are used.
As a packaging material laminate used for such a package, for example, a laminate having a configuration such as polyethylene terephthalate (PET) resin film / aluminum foil / polyamide (PA) resin film / unstretched polyethylene (PE) resin film The body 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, when an adhesive or an anchor coat agent is used for pasting the sealant layer, it may react with the liquid content filled in the packaging bag and adversely affect the components of the content. Further, the dry lamination method using an adhesive, the film sand method using an anchor coating agent, and the extrusion lamination method have problems in terms of environmental measures and energy saving measures because organic solvents are used. Furthermore, since there is a risk of migration of residual solvent and low molecular components, there is a problem that the influence of contamination on the contents is unavoidable.
In addition, when polyethylene-based resin is melt-extruded to the sealant layer by extrusion laminating method, the polyethylene-based resin decomposes and a polyethylene odor adheres, so the packaging material lamination for filling contents such as foods that dislike odor There was a problem using it as a body.
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 the required adhesive strength without using an adhesive or an anchor coat agent for bonding a sealant layer. Yes.

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.
Thus, in the prior art, different films were produced using a packaging material laminate and a method for producing a packaging material laminate in which a sealant layer was laminated without using an adhesive and an anchor coat agent. The package was not known.

  The present invention has been made in view of the above. That is, an object of the present invention is to provide a method for producing a packaging material laminate in which a sealant layer is laminated without using an adhesive and an anchor coating agent, a packaging material laminate, and a packaging body produced using the packaging material laminate. Is an issue.

In the present invention, in order to solve the above-mentioned problems, a gas barrier comprising a thermoplastic resin film having a thin film layer of a metal, a metal compound, an inorganic compound, an organic compound or an organic / inorganic hybrid, or a thermoplastic resin film having a gas barrier property on the film itself. A method for producing a packaging material laminate including a layer and a base material having heat sealability, the base material having heat sealability and a thermoplastic resin film adjacent thereto (the film itself has gas barrier properties) Production of a packaging material laminate in which a thermoplastic resin film or another thermoplastic resin film may be bonded by thermocompression bonding without applying an adhesive and an anchor coating agent. Provide a method.
A heat-adhesive modified layer is formed on the adhesive surface of the thermoplastic resin film by surface modification using an atmospheric pressure plasma processing apparatus, and an air corona treatment (unstretched) is applied to the adhesive surface of the heat-sealable substrate. This is a method for producing a packaging material laminate in which atmospheric pressure plasma treatment is essential for polypropylene.
In addition, a packaging material in which a thermoadhesive modified layer is formed by surface modification using an atmospheric pressure plasma processing apparatus on both the adhesive surface of the thermoplastic resin film and the adhesive surface of the heat-sealable substrate. A method for producing a laminate is provided.

  In order to solve the above problems, the present invention provides one or more gas barrier layers selected from the group consisting of metal foil, metal or metal oxide vapor-deposited films, and resin composition layers having gas barrier properties, and heat sealing. A packaging material laminate comprising a first base material having a property, wherein the packaging material laminate comprises the first base material exposed on one side thereof and a thermoplastic resin film adjacent thereto. In the step of laminating the first base material and the second base material, the second base material consisting of is laminated without an adhesive and an anchor coating agent. Either one of the adhesive surface of the first base material and the adhesive surface of the second base material is provided with a thermal adhesion modified layer by surface modification using an atmospheric pressure plasma processing apparatus, Does not have an air corona-treated surface modification layer. Preparing the first base material and the second base material, the first base material and the second base material, the thermoadhesive modified layer of the first base material and the surface modified layer facing each other, and bonding; There is provided a method for producing a packaging material laminate, wherein the first base material and the second base material are bonded together by thermocompression bonding without applying an agent and an anchor coat agent.

  In order to solve the above problems, the present invention includes at least one gas barrier layer selected from the group consisting of a metal foil, a metal or metal oxide deposition film, and a resin composition layer having gas barrier properties; A method for producing a packaging material laminate including a first base material having heat sealability, wherein the packaging material laminate comprises the first base material exposed on one side thereof and a thermoplastic adjacent thereto. In the step of laminating the first base material and the second base material, the second base material made of a resin film is laminated without using an adhesive and an anchor coat agent. In both of the first substrate and the second substrate, a thermal adhesion modified layer is formed by surface modification using an atmospheric pressure plasma processing apparatus. Preparing the first base material and the second base material; The heat-adhesive modified layers of the base material and the second base material are made to face each other, and thermocompression-bonded without applying an adhesive and an anchor coat agent, and the first base material and the second base material The manufacturing method of the packaging material laminated body characterized by bonding a material.

  In the manufacturing method of said packaging material laminated body, when bonding said 1st base material and said 2nd base material, by surface modification of the resin film beforehand using an atmospheric pressure plasma processing apparatus. The second base material and / or the first base material on which a heat adhesion modified layer is formed, and a reference film which is the same or different type of thermoplastic resin film and is subjected to air corona treatment. The surface of the second base material and / or the first base material on which the heat adhesion modified layer is formed is opposed to the air corona treated surface of the reference film that has been subjected to the air corona treatment. Then, the test laminate is obtained by thermocompression bonding without applying the anchor coat agent, and then the adhesive force on the bonding surface of the test laminate is measured to determine the second substrate and / or the first Confirm the quality of the heat-adhesive modified layer on the substrate. It is preferable to.

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

The first substrate is unstretched polyethylene (PE) or unstretched polypropylene (CPP), and the second substrate is polyethylene terephthalate (PET), polyamide (PA), polyethylene naphthalate (PEN). , Preferably one selected from the group consisting of polyacrylonitrile (PAN), polycarbonate (PC), polyimide (PI), polyvinyl chloride (PVC), and ethylene-vinyl alcohol copolymer (EVOH). .
When the second substrate is made of a thermoplastic resin film having gas barrier properties, it can also serve as the gas barrier layer.

  A step of laminating each layer on the outer side of the second base material with the second base material when the first base material is the inner surface side of the package in the laminate; When it implements prior to the pasting process by the thermocompression bonding with the second base material, after the pasting process, the laminated body is 10 to 1 month at room temperature, or 1 to 3 at 40 to 60 ° C. It is preferable to include an aging step that is allowed to stand for days.

  Moreover, this invention provides the packaging material laminated body manufactured by the manufacturing method of said packaging material laminated body.

  In addition, the present invention provides a packaging body, wherein the packaging material laminate is manufactured such that the first base material having heat sealability is an inner surface side as a sealant layer. To do.

  The present invention also provides at least one gas barrier layer selected from the group consisting of a metal foil, a deposited film of metal or metal oxide, and a resin composition layer having gas barrier properties, and a first having heat sealing properties. A packaging material laminate comprising: the first base material exposed on one side thereof; and a second base material comprising a thermoplastic resin film adjacent thereto. Are laminated without using an adhesive and an anchor coat agent, and either one of the adhesive surface of the first base material and the adhesive surface of the second base material has an atmospheric pressure plasma. A heat-adhesive modified layer is formed by surface modification using a processing apparatus, the other is subjected to air corona treatment, and the first base material and the second base material are adhesive and anchor coats. It is bonded by thermocompression bonding without applying the agent. To provide a packaging material laminate, characterized in that.

  The present invention also provides at least one gas barrier layer selected from the group consisting of a metal foil, a deposited film of metal or metal oxide, and a resin composition layer having gas barrier properties, and a first having heat sealing properties. A packaging material laminate comprising: the first base material exposed on one side thereof; and a second base material comprising a thermoplastic resin film adjacent thereto. Are laminated without using an adhesive and an anchor coat agent, and an atmospheric pressure plasma processing apparatus is used on both the adhesive surface of the first base material and the adhesive surface of the second base material. A heat-adhesive modified layer is formed by the surface modification used, and the first base material and the second base material are bonded by thermocompression bonding without applying an adhesive and an anchor coating agent. A laminated packaging material characterized by To.

The first substrate is unstretched polyethylene (PE) or unstretched polypropylene (CPP), and the second substrate is polyethylene terephthalate (PET), polyamide (PA), polyethylene naphthalate (PEN). , Preferably one selected from the group consisting of polyacrylonitrile (PAN), polycarbonate (PC), polyimide (PI), polyvinyl chloride (PVC), and ethylene-vinyl alcohol copolymer (EVOH). .
When the second substrate is made of a thermoplastic resin film having gas barrier properties, it can also serve as the gas barrier layer.

  In addition, the present invention provides a packaging body, wherein the packaging material laminate is manufactured such that the first base material having heat sealability is an inner surface side as a sealant layer. To do.

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 the low molecular component derived from 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.

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 the 3rd example of the packaging material laminated body concerning this invention. It is a schematic sectional drawing which shows the 4th 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 to 4 are each a schematic cross-sectional view showing an example of a packaging material laminate according to the present invention, each of which includes a metal foil, a metal or metal oxide vapor deposition film, and a resin composition layer having gas barrier properties. One surface of the packaging material laminates 10 to 13 including one or more gas barrier layers selected from the inside comprises, in order from the top, a first base material 1 having heat sealability and a thermoplastic resin film. The second base material 3 or 7 is laminated at least, and the thermoplastic resin film 3 or 7 and the base material 1 having heat sealability are heated without applying an adhesive and an anchor coating agent. It is the packaging material laminated bodies 10-13 formed by crimping and bonding.

  In the packaging material laminate 10 according to the first example shown in FIG. 1, the other resin film 6 and the gas barrier property (when the first base material 1 is set as the upper side) on the lower side of the thermoplastic resin film 3 ( Alternatively, metal foils 5 having further light shielding properties are bonded to each other via the adhesive layer 4. In this example, the metal foil 5 is a gas barrier layer. Instead of metal foil, a thermoplastic resin film having gas barrier properties can also be used. Although not particularly shown, for example, a printed layer can be provided between the other resin film 6 and the metal foil 5. When the metal foil 5 has an opening, a printing layer can be provided between the thermoplastic resin film 3 and the metal foil 5.

In the packaging material laminate 11 according to the second example shown in FIG. 2, the second base material 7 is made of a thermoplastic resin film 7 having gas barrier properties, and the second base material 7 having gas barrier properties and others. The resin film 6 is bonded through an adhesive layer 4. In this example, the second substrate 7 also serves as a gas barrier layer. Although not particularly shown, for example, a printed layer can be provided between the other resin film 6 and the base material 7.
In the packaging material laminate 12 according to the third example shown in FIG. 3, the gas barrier layer 8 made of a thin film layer such as a vapor-deposited film of metal or metal oxide or a coating film of a resin composition having gas barrier properties is used as another resin. The other resin film 6 formed on the upper surface of the film 6 and having the gas barrier layer 8 and the second substrate 3 are bonded together with an adhesive layer 4 interposed therebetween. Although not particularly shown, for example, a printing layer can be provided between the base material 3 and another resin film 6 having the gas barrier layer 8.
In the packaging material laminate 13 according to the fourth example shown in FIG. 4, the gas barrier layer 8 composed of a thin film layer such as a metal or metal oxide vapor-deposited film or a resin composition coating film having gas barrier properties is provided in the second layer. The second base material 3 formed on the lower surface of the base material 3 and having the gas barrier layer 8 and the other resin film 6 are bonded together with an adhesive layer 4 interposed therebetween. Although not particularly illustrated, for example, a printing layer may be provided between the other resin film 6 and the base material 3 having the gas barrier layer 8.
The present invention is not limited to the above example, and two or more gas barrier layers can be provided in the laminate.

A thermoadhesive modified layer is formed on the adhesive surface 2 of the thermoplastic resin film 3 or 7 by surface modification using an atmospheric pressure plasma processing apparatus, and an air corona is applied to the adhesive surface 2 of the substrate 1 having heat sealability. It has been processed. The adhesive surface 2 is bonded by thermocompression bonding without applying an adhesive and an anchor coat agent.
The surface of the thermoplastic resin film 3 or 7 on which the heat-adhesive property-modified layer is formed and the air corona-treated surface of the base material 1 having heat sealing properties are opposed to each other, and an adhesive and an anchor coating agent are applied. Without carrying out thermocompression bonding by holding at a predetermined heating temperature and applied pressure, the first substrate 1 and the second substrate 3 or 7 in the packaging material laminates 10 to 13 according to the present invention Bonding can be obtained.

  In addition, a thermoadhesive modified layer is formed on both the adhesive surface 2 of the thermoplastic resin film 3 or 7 and the adhesive surface 2 of the base material 1 having heat sealability by surface modification using an atmospheric pressure plasma processing apparatus. Then, the surface of the thermoplastic resin film 3 or 7 on which the heat-adhesive modified layer is formed and the surface on which the heat-adhesive modified layer of the base material 1 having heat-sealing properties are opposed, The first base material 1 and the first base material 1 in the packaging material laminates 10 to 13 according to the present invention are obtained by performing thermocompression bonding while holding at a predetermined heating temperature and pressure without applying an adhesive and an anchor coating agent. It is also possible to obtain bonding with the two base materials 3 or 7.

As the thermoplastic resin film 3, polyethylene terephthalate (PET) resin film, polyamide (PA) resin film, polyethylene naphthalate (PEN) resin film, polyacrylonitrile (PAN) resin film, polycarbonate (PC) resin film, polyimide (PI) ) Resin film.
Examples of the thermoplastic resin film 7 having gas barrier properties include a polyvinyl chloride (PVC) resin film or an ethylene-vinyl alcohol copolymer (EVOH) resin film.
Moreover, as the base material 1 which has heat-sealability, an unstretched polyethylene (PE) resin film, an unstretched polypropylene (CPP) resin film, etc. are mentioned.
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 10-13, the base material 1 which has heat-sealability, and the thermoplastic resin film 3 or 7 are laminated | stacked without using an adhesive agent and an anchor coating agent.
Since the base material 1 having heat sealability is laminated on one resin film of the packaging material laminates 10 to 13, the packaging material laminates 10 to 13 are cut into predetermined shapes and dimensions, A package can be produced by heat-sealing the base material 1 having heat sealability as the inner surface side.

FIG. 5 shows an example of a packaging material laminate 20 according to the prior art, one selected from the group consisting of a metal foil, a metal or metal oxide deposited film, and a resin composition layer having gas barrier properties. On one surface of the packaging material laminate 20 including the above gas barrier layer, at least a base material 21 having heat sealability and a thermoplastic resin film 23 are laminated in order from the top, and the thermoplastic resin film. 23 and the base material 21 which has the said heat-sealability are the packaging material laminated bodies 20 formed by adhere | attaching using an adhesive agent.
On the lower side of the thermoplastic resin film 23, another resin film 26 and a metal foil 25 having gas barrier properties or light shielding properties are bonded together with an adhesive layer 24 interposed therebetween.

By the way, in the packaging material laminate of the present invention, as the thermoplastic resin film 3, for example, a polyethylene terephthalate (PET) resin film, and as the base material 1 having heat sealability, for example, an unstretched polyethylene (PE) resin film. There are the following three combinations.
(1): (modified PET) / (air corona-treated PE)
(2): (Modified PET) / (Modified PE)
(3): (Air corona-treated PET) / (Modified PE)
Here, the modified PET is a polyethylene terephthalate (PET) resin having a thickness of 10 to 500 μm on which at least one surface is formed with a thermal adhesion modified layer by surface modification using an atmospheric pressure plasma treatment apparatus. It is a film.
Air corona-treated PET is a polyethylene terephthalate (PET) resin film having a thickness of 10 to 500 μm and subjected to air corona treatment.
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.

Since the packaging material laminates 10 to 13 of the present invention have the base material 1 having heat sealability laminated on one surface, they can be suitably used for packaging. For example, a bag body can be obtained by folding the packaging material laminate 10 into two in order to use unstretched polyethylene (PE) as a heat seal layer, and then heat-sealing the three sides.
Also, the two packaging material laminates 10 to 13 cut to a predetermined size are stacked, the both end portions are heat sealed, and the bottom packaging material laminates 10 to 13 are heat sealed. Thus, a standing pouch type self-supporting package can be obtained.
In addition, in a refilling packaging container, a self-standing standing pouch is provided, and furthermore, a packaging container that simplifies the refilling operation of contents can be obtained by arranging spouts in various easy-to-pour shapes. Can do.
In addition, for use in applications such as electronic parts, medical parts, medical equipment parts, precision machine parts, etc., a base film with cleanliness maintained is used in the work environment in a cleanroom with special cleanliness control. 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 the thermoplastic resin films 3 and 7 are bonded to the base material 1 having heat sealability, the thermal adhesiveness modification is performed in advance by surface modification of the resin film using an atmospheric pressure plasma processing apparatus. The thermoplastic resin films 3 and 7 and / or the heat-sealable base material 1 on which a layer is formed and a specific film which is the same or different kind of thermoplastic resin film and subjected to air corona treatment are used. The quality of the surface on which the heat-adhesive modified layer is formed by surface modification is determined by an atmospheric pressure plasma processing apparatus. That is, the surface of the thermoplastic resin films 3 and 7 and / or the heat-sealing base material 1 on which the heat adhesion modified layer is formed, and the specific film (reference film) formed by the air corona treatment. Adhesive strength when thermocompression bonding is carried out without applying an adhesive and an anchor coating agent with the air corona treated surfaces facing each other, the JIS K 6854-1 “Adhesive Peeling Adhesive Strength Test Method Part 1: 90 degrees It is necessary that surface modification using an atmospheric pressure plasma processing apparatus is performed so that a value measured by a measuring method defined in “peeling” is equal to or greater than a predetermined value.
The reference film is only used for determining the quality of the surface, and is not finally included in the product laminate. For example, when the first base material and / or the second base material is a long film, bonding with a reference film is performed in a part of the longitudinal direction, and the quality of the surface modification processing conditions is good. After confirming, the method of performing pasting of the 1st substrate and the 2nd substrate continuously is mentioned. In this case, the portion where the laminate is bonded to the reference film is preferably cut (removed) from the product.
The pass / fail confirmation process by bonding with the reference film does not have to be performed every time when the packaging material laminate is produced. For example, the first base material and / or the second base material subjected to the atmospheric pressure plasma treatment are used. When changing the type of base material, when changing the processing conditions of atmospheric pressure plasma, when cleaning the atmospheric pressure plasma processing equipment or replacing parts, etc., it is possible to carry out pass / fail confirmation process as necessary desirable.

  In the prior art, by surface modification using atmospheric pressure plasma treatment, certain functional groups such as COOH groups and OH groups are formed on the film surface, and can be firmly laminated and bonded at low temperatures. However, there is no description that defines a standard for judging a preferable treatment 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, The present invention has been achieved.

  In atmospheric pressure plasma processing, processing conditions such as time for applying plasma to the film surface, applied power, frequency, etc., for example, to search for plasma processing conditions for polyethylene terephthalate (PET) resin film, PET The surface of the resin film on which the heat adhesion modified layer is formed is opposed to the air corona-treated surface of an air-corona-treated unstretched polyethylene (PE) resin film (Tamapoly Corporation unstretched polyethylene film, trade name: SK615P). 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” With the measurement method specified in “Test method Part 1: 90 degree peeling” at a speed of 5 mm / min. If the surface modification using the atmospheric pressure plasma processing apparatus is performed so that the strength when it is applied is 5.9 N / 25.4 mm or more, a packaging material laminate usable for the packaging is obtained. be able to.

  In addition, the surface on which the heat-adhesive modified layer of the polyamide (PA) resin film subjected to the atmospheric pressure plasma treatment is formed is an air-corona-treated unstretched polyethylene (PE) resin film (unstretched polyethylene film manufactured by Tamapoly Corporation, Product name: SK615P) facing the air corona treatment surface, without applying an adhesive and an anchor coating agent, 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, 9.8 N / 25.4 mm or more as the strength when peeled at a speed of 5 mm / min by the measurement method specified in JIS K 6854-1 “Adhesive peel adhesion strength test method Part 1: 90 degree peel” If surface modification using an atmospheric pressure plasma processing apparatus has been performed, a packaging material laminate that can be used for packaging is obtained. It can be.

(Resin film)
As the thermoplastic resin film 3 used in the packaging material laminate of the present invention, a polyethylene terephthalate (PET) resin film, a polyamide (PA) resin film, a polyethylene naphthalate (PEN) resin film, a polyacrylonitrile (PAN) resin film, Examples thereof include a polycarbonate (PC) resin film and a polyimide (PI) resin film. Examples of the thermoplastic resin film 7 having gas barrier properties include a polyvinyl chloride (PVC) resin film and an ethylene-vinyl alcohol copolymer (EVOH) resin film. Examples of the base material 1 having heat sealability include an unstretched polyethylene (PE) resin film and an unstretched polypropylene (CPP) resin film.
Examples of the thermoplastic resin films 1, 3, and 7 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, polyvinyl chloride (PVC) resin, and ethylene-vinyl. Alcohol copolymer (EVOH), polyethylene naphthalate (PEN) resin, polyacrylonitrile (PAN) resin, polycarbonate (PC) resin, polyimide (PI) resin, unstretched polyethylene (PE) resin, unstretched polypropylene (CPP) resin For example, a resin film. The melting points of these thermoplastic resins are polyethylene terephthalate (252 ° C.), polyamide (220 ° C.), polyvinyl chloride (none), ethylene-vinyl alcohol copolymer (160 to 190 ° C.), polyethylene naphthalate (about 270 ° C.), polyacrylonitrile (none), polycarbonate (none), polyimide (none), unstretched polyethylene (105-140 ° C.), unstretched polypropylene (130-165 ° 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 base material 1 having heat sealability in the case of lamination needs to be lower than the melting point of the thermoplastic resin films 3 and 7. When thermocompression bonding is performed at a temperature higher than the melting point of the thermoplastic resin films 3 and 7, there is a problem that the resin adheres to the heating roll and the surface of the 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 thermoplastic resin films 3 and 7 and the base material 1 having heat sealability used for the packaging material laminates 10 to 13 of the present invention are 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 manufacturing a packaging material laminate according to the present invention, when a laminated film is produced by bonding surface-modified resin films together by thermocompression bonding, the laminated resin film is wound as a roll body. It is necessary to consider that the total thickness does not exceed 500 μm.
In addition, when the thickness of the 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 of producing the packaging material laminates 10 to 13 of the present invention, the following (1) to (3) are used to laminate the thermoplastic resin films 3 and 7 and the base material 1 having heat sealing properties together. ).
(1) The surface of the thermoplastic resin films 3 and 7 is subjected to a surface treatment using an atmospheric pressure plasma treatment apparatus to form a heat-adhesive modified layer, or a corona discharge treatment (air corona treatment in an air atmosphere). ) To perform surface treatment.
(2) The surface of the substrate 1 having heat sealability is subjected to surface treatment using an atmospheric pressure plasma treatment apparatus to form a heat-adhesive modified layer, or corona discharge treatment in an air atmosphere (air corona Surface treatment. In addition, when the base material 1 which has heat-sealing property consists of an unstretched polypropylene, atmospheric pressure plasma processing is essential.
(3) Superimposing the surface of the base material 1 having heat sealability on the surface of the thermoplastic resin films 3 and 7 on which the heat-adhesive reforming layer is formed, and by thermocompression bonding Laminate.
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 performing surface treatment on the surface of the film of the first base material by corona discharge treatment (air corona treatment) in an air atmosphere, in (2), Surface treatment is performed 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 to 13 of the present invention, the two resin films to be bonded together by thermocompression bonding include, as the thermoplastic resin films 3 and 7, a polyethylene terephthalate (PET) resin film, a polyamide (PA) resin film, Polyvinyl chloride (PVC) resin film, ethylene-vinyl alcohol copolymer (EVOH) resin film, polyethylene naphthalate (PEN) resin film, polyacrylonitrile (PAN) resin film, polycarbonate (PC) resin film, polyimide (PI) Examples of the base material 1 that is a resin film or the like and has heat sealability include an unstretched polyethylene (PE) resin film and an unstretched polypropylene (CPP) resin film.
The other resin film 6 may be a film made of the same material as or different from the thermoplastic resin films 3 and 7 or the base material 1 having heat sealability.
When laminating is performed by heat laminating, the two resin films can be laminated by thermocompression bonding in a superposed state.
The adhesive used for the adhesive layer 4 is not particularly limited, and can be appropriately selected and used depending on the material of the adherend, such as urethane-based, epoxy-based, and carboxylic acid-modified polyolefin resin. The adhesive may use an organic solvent, but is preferably dried well before and after lamination to reduce the residual solvent as much as possible.

Although the layer structure of a packaging material laminated body is not specifically limited, For example, the following structural examples are mentioned. In the following examples, the right side shows the sealant layer.
[Configuration Example of Packaging Material Laminate 10 shown in FIG. 1]
(1-1) PET / adhesive layer / aluminum foil / adhesive layer / PA / adhesive surface / PE
(1-2) PET / adhesive layer / aluminum foil / adhesive layer / PA / adhesive surface / CPP
[Configuration Example of Packaging Material Laminate 11 shown in FIG. 2]
(2-1) PA / adhesive layer / EVOH / adhesive surface / PE
(2-2) PA / adhesive layer / EVOH / adhesive surface / CPP
(2-3) PA / adhesive layer / PVC / adhesive surface / PE
(2-4) PA / adhesive layer / PVC / adhesive surface / CPP
[Configuration example of the packaging material laminate 12 shown in FIG. 3]
(3-1) PET / silica vapor deposited film / adhesive layer / PA / adhesive surface / PE
(3-2) PET / silica vapor deposition film / adhesive layer / PA / adhesive surface / CPP
(3-3) PET / gas barrier coating film / adhesive layer / PA / adhesive surface / PE
(3-4) PET / gas barrier coating / adhesive layer / PA / adhesive surface / CPP
[Configuration example of the packaging material laminate 13 shown in FIG. 4]
(4-1) PA / adhesive layer / aluminum deposited film / PET / adhesive surface / PE
(4-2) PA / adhesive layer / aluminum deposited film / PET / adhesive surface / CPP

The surface modification treatment for the two resin films used in the packaging material laminate of the present invention may be performed first as long as it is a stage prior to lamination. Further, the surface modification treatment may be performed simultaneously or in parallel on the two films to be laminated.
Moreover, this invention provides the packaging material laminated body by which the sealant layer was laminated | stacked without using an adhesive agent and an anchor coating agent, and a package produced using the same.
Therefore, an adhesive may be used to bond the resin film and the metal foil other than the sealant layer.

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

(Aging process)
In the present invention, when the first base material to be the sealant layer in the package is the inner surface side, each layer on the outer side of the second base material (the second base material 3, in the laminate of FIGS. 1 to 4). 7, a step of laminating a metal foil 5 or other resin film 6, etc. below the second base material (further, a step using an organic solvent such as a printing step on the base material, The step of drying the organic solvent used in the step) is performed prior to the thermocompression bonding step of the first substrate and the second substrate, and the bonding step by thermocompression is performed in the production of the laminate. When it comes to the last, it is preferable to include the aging process which leaves a laminated body for 10 days-1 month at normal temperature, or 1-3 days from 40-60 degreeC after a thermocompression bonding process. Thereby, while being able to increase the adhesive force between a 1st base material and a 2nd base material, drying after dry lamination can fully be performed, and the inside of a laminated body (especially inside a sealant layer) remains. The solvent can be reduced as much as possible.
In addition, even if a thermocompression bonding process is not the last process of laminated body manufacture, if needed, it is possible to implement the said aging process in the middle of laminated body manufacture.

  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.
・ Boil retort test: 200 ml of water was filled in a four-sided bag (130 mm × 170 mm), the boil condition was 97 ° C. × 40 min, the retort condition was 121 ° C. × 30 min, and the appearance of the laminate was evaluated. .
・ Content resistance suitability test: 200ml filled into a four-sided bag (130mm x 170mm) using contents that degrade the performance of the adhesive and anchor coating agent, and a predetermined number of days have passed (1 month storage at 50 ° C) Later, the adhesive strength of the laminate was evaluated.

(Checking the quality of the heat-adhesive modified layer)
When producing a packaging material laminate according to the present invention, first, various thermoplastic resin films were subjected to surface modification using an atmospheric pressure plasma treatment apparatus, and then the quality of the thermal adhesive modified layer was confirmed. A prepared substrate 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 manufacturing method of the packaging material laminate according to the present invention, the base material A on which the heat adhesion modified layer by surface modification is formed in advance using the atmospheric pressure plasma processing apparatus to be used, It is necessary to confirm whether or not the formation state of the heat-adhesive modified layer 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 100 μm (Tamapoly Co., Ltd. unstretched polyethylene film, trade name: SK615P), 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, the surface-modified resin film of the obtained surface modification examples 1, 2, 5, 6, 9, and 10 and the air-corona-treated thermoplastic resin film were used with an adhesive or an anchor coating agent. However, after laminating only by thermocompression bonding to obtain a laminated body of the heat seal layer, the aluminum foil and the PET resin film were further laminated through the adhesive layer, and Examples 1 to 3 and comparison The packaging material laminated body of Examples 1-3 was produced.
Also, the surface-modified resin films of the surface modification examples 7 and 8 obtained and the air-corona-treated thermoplastic resin film were bonded only by thermocompression bonding without using an adhesive or an anchor coating agent. Then, after obtaining a laminated body of the heat seal layer, the PA resin film was further bonded via an adhesive layer to produce a packaging material laminated body of Examples 4 and 5.
Furthermore, in order to compare with the laminated body produced by this invention, it bonded by the dry lamination system using the all process adhesive agent which is a prior art, and produced the laminated body of the comparative example 4. FIG.

Example 1
The surface on which the heat-adhesive modified layer of the polyamide (PA) resin film of the surface modification example 1 is formed, and a commercially available air-corona-treated unstretched polyethylene (PE) resin film (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. The laminated body of the heat seal layer thus obtained was bonded to a 9 μm thick aluminum foil and a 12 μm thick polyethylene terephthalate (PET) resin film with an adhesive to obtain a packaging material laminate of Example 1. 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, A packaging material laminate of Comparative Example 1 was obtained in the same manner as in Example 1, except that the laminate of the heat seal layer to which was attached was used. 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 heat seal layer laminate in which the air corona-treated surface of the film, trade name: SK615P) 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 heat seal layer 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 5)
The surface of the surface modification example 7 on which the heat-adhesive modified layer of the polyvinyl chloride (PVC) resin film is formed, and an unstretched polyethylene (PE) resin film treated with air corona (unstretched manufactured by Tamapoly Co., Ltd.) The air corona-treated surface of polyethylene film, trade name: SK615P) is heat-pressed with a heating roll at a speed of 5 m / min, a temperature of 140 ° C., and a pressure of 0.23 MPa without applying an adhesive and an anchor coating agent. A 15 μm thick polyamide (PA) resin film was bonded to the heat seal layer laminate via an adhesive to obtain a packaging material laminate of Example 5. Furthermore, after producing the packaging container of a four-side seal bag using the packaging material laminated body of obtained Example 5, various tests regarding the packaging container were performed.

Example 4
The surface on which the heat-adhesive modified layer of the ethylene-vinyl alcohol copolymer (EVOH) resin film of the surface modification example 8 was formed, and an unstretched polyethylene (PE) resin film (Tamapoly Co., Ltd.) treated with air corona Company unstretched polyethylene film, product name: SK615P) air corona-treated surface and heated 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. A 15 μm thick polyamide (PA) resin film was bonded to the laminate of the heat-sealed heat-bonded layer via an adhesive to obtain a packaging material laminate of Example 4. Furthermore, after producing the packaging container of a four-side seal bag using the packaging material laminated body of obtained Example 4, various tests regarding the packaging container were performed.

(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. The laminate of the heat seal layer thus obtained was bonded with an aluminum foil having a thickness of 9 μm and a polyethylene terephthalate (PET) resin film having a thickness of 12 μm via an adhesive 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 heat seal layer 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.

(Comparative Example 4)
According to the prior art, an air corona-treated surface of a polyamide (PA) resin film having a thickness of 15 μm (a biaxially stretched polyamide film manufactured by Kojin Co., Ltd .; trade name: Bonyl W) 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 laminate of heat seal layers was obtained.
Further, similarly to Example 1, the obtained heat seal layer laminate of Comparative Example 4 was bonded with an aluminum foil and a PET resin film via an adhesive layer, and the packaging material laminate of Comparative Example 4 was laminated. Got the body. 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 5 and Comparative Examples 1 to 4 obtained as described above, a packaging container of a standing type or a four-sided seal bag was prepared, 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 structures of the packaging material laminates of Examples 1 to 5 and Comparative Examples 1 to 4 which are packaging material laminates according to the present invention.

Table 3 was performed about the packaging type (packaging container) of the standing type or the four-sided seal bag produced using the packaging material laminated body of Examples 1-5 which are packaging material laminated bodies by this invention, and Comparative Examples 1-4. It is the result of various tests.
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 5 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 5 which are packages according to the present invention are compared, There is no significant difference.
Therefore, the packaging material laminate according to the present invention has the same level of properties as the packaging material laminate by the dry lamination method using the adhesive according to the prior art, and there is no problem as a constituent material of the packaging body (packaging container). It is possible to use without generating.

Table 4 shows the results of the boil / retort test. The boil test was performed on the packaging containers of Examples 1, 2, and 4, and the retort test was performed on the packaging container of Example 3.
In all cases, the occurrence of the delamination (peeling from the bonding surface) phenomenon has not occurred, and the durability is the same as that of a packaging container produced using a laminate produced by a dry lamination method using an adhesive according to a conventional conventional technique. It has sex.

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)
To determine the quality of the surface on which the thermal adhesion modified layer is formed by surface modification with an atmospheric pressure plasma treatment device, select a specific film as a reference and laminate the polyamide (PA) resin film A reference value is set that guarantees that the adhesive strength when used as a body 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 reference film, for example, a commercially available air-corona-treated unstretched polyethylene (PE) resin film (Tamapoly Co., Ltd. unstretched polyethylene film, trade name: SK615P) facing the air corona-treated surface and holding for 10 seconds at a temperature of 160 ° C. and a pressure of 0.4 MPa without applying an adhesive and an anchor coating agent. The adhesive strength when thermocompression bonding was performed was 9.8 N / 25. The value measured by the measurement method defined in JIS K 6854-1, “Adhesive Peeling Adhesive Strength Test Method Part 1: 90 ° Peeling”. 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 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.

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. It is possible to effectively perform the atmospheric pressure plasma treatment by determining whether the thermal adhesive property modified layer is in a good state.
Moreover, according to this invention, the manufacturing method of a laminated body bonded without using an adhesive agent and an anchor coat agent, a laminated body, and the packaging container produced using it 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-sealability (first base material), 2 ... Adhesive surface, 3, 23 ... Thermoplastic resin film (second base material), 4, 24 ... Adhesive layer, 5, 25 ... gas barrier layer (metal foil), 6, 26 ... other resin films, 7 ... gas barrier layer (second base material having gas barrier properties), 8 ... gas barrier layer (thin film layer such as vapor deposition film and coating film), 10-13 ... Packaging material laminate of the present invention, 20 ... Packaging material laminate according to the prior art.

Claims (14)

One or more gas barrier layers 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, and a first base material having heat sealability. A method for producing a packaging material laminate,
In the packaging material laminate, the first base material exposed on one side thereof and the second base material made of a thermoplastic resin film adjacent to the first base material are laminated without using an adhesive and an anchor coating agent. And
In the step of bonding the first base material and the second base material, either one of the adhesive surface of the first base material and the adhesive surface of the second base material is large. The first base material and the second substrate, in which a thermal adhesion modified layer is formed by surface modification using an atmospheric pressure plasma processing apparatus, and on the other side, a surface modified layer subjected to air corona treatment is formed. A material is prepared, and the heat-adhesive modified layer and the surface-modified layer 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 the manufacturing method of the packaging material laminated body characterized by bonding the said 1st base material and the said 2nd base material. One or more gas barrier layers 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, and a first base material having heat sealability. A method for producing a packaging material laminate,
In the packaging material laminate, the first base material exposed on one side thereof and the second base material made of a thermoplastic resin film adjacent to the first base material are laminated without using an adhesive and an anchor coating agent. And
In the step of bonding the first base material and the second base material, atmospheric pressure plasma is applied to both the adhesive surface of the first base material and the adhesive surface of the second base material. The first base material and the second base material in which a thermal adhesion modified layer is formed by surface modification using a processing apparatus are prepared, and the first base material and the second base material are prepared. The heat-adhesive modified layers are opposed to each other, and are bonded by thermocompression without applying an adhesive and an anchor coat agent, thereby bonding the first base material and the second base material. A method for producing a packaging material laminate.   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 a reference film which is the same or different type of thermoplastic resin film and subjected to air corona treatment, the second base material and / or Thermocompression bonding without applying an adhesive and an anchor coat agent, with the surface of the first base material on which the heat adhesion modified layer is formed facing the air corona treatment surface of the air corona treatment reference film After obtaining the test laminate, the adhesive strength on the bonding surface of the test laminate is measured to form the second base material and / or the thermal adhesion modified layer of the first base material. 3. The state is checked for quality, according to claim 1 or 2, Method for producing a mounting of the packaging material laminate. When the base material on which the thermal adhesion modified layer is formed using an atmospheric pressure plasma treatment apparatus is a polyamide (PA) resin film, an unstretched polyethylene (PE) resin film that has been subjected to air corona treatment is used as the reference film. The adhesive strength when heated and pressed 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” Confirm that the value measured by the specified measurement method 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 film as the 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” Confirm that the value measured by the measurement method specified in 5.9 is 5.9 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 a polyethylene terephthalate (PET) resin film, an unstretched polyethylene (PE) resin film that has been subjected to air corona treatment as the 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” Confirm that the value measured by the measurement method specified in 5.9 is 5.9 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 a polyvinyl chloride (PVC) resin film, an unstretched polyethylene (PE) resin treated with air corona as the reference film Adhesive strength when film is used and held for 10 seconds at a temperature of 140 ° C. and an applied 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 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 unstretched polyethylene subjected to air corona treatment as the reference film Adhesive strength when (PE) resin film is used and held for 10 seconds at a temperature of 160 ° C. and a pressure of 0.4 MPa is JIS K 6854-1 “Adhesive Peeling Bond Strength Test Method Part 1 : The value measured by the measurement method specified in “90 degree peeling” 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 processing apparatus is an unstretched polypropylene (CPP) resin film, an air corona-treated polyethylene terephthalate (PET) resin film as the reference film JIS K 6854-1 “Adhesive Peeling Adhesive Strength Test Method Part 1: 90 degree peeling” It confirms that the value measured with the measuring method prescribed | regulated to 5.9N / 25.4mm or more is confirmed, The manufacturing method of the packaging material laminated body of Claim 3 characterized by the above-mentioned.   The first substrate is unstretched polyethylene (PE) or unstretched polypropylene (CPP), and the second substrate is polyethylene terephthalate (PET), polyamide (PA), polyethylene naphthalate (PEN). , One selected from the group consisting of polyacrylonitrile (PAN), polycarbonate (PC), polyimide (PI), polyvinyl chloride (PVC), and ethylene-vinyl alcohol copolymer (EVOH) The manufacturing method of the packaging material laminated body in any one of Claim 1 to 4.   The method for producing a packaging material laminate according to any one of claims 1 to 4, wherein the second base material is made of a thermoplastic resin film having gas barrier properties and also serves as the gas barrier layer.   The step of laminating each layer on the outer side of the second base material with the second base material when the first base material is the inner surface side of the package in the laminated body is the first base material. Prior to the bonding step by thermocompression bonding with the second base material, and after the bonding step, the laminate is at room temperature for 10 days to 1 month, or at 40 to 60 ° C. for 1 to 3 days. The manufacturing method of the packaging material laminated body in any one of Claim 1 to 6 including the aging process to leave still.   The packaging material laminated body manufactured by the manufacturing method of the packaging material laminated body in any one of Claim 1 to 7.   A packaging body, wherein the packaging material laminate according to claim 8 is manufactured so that the first base material having heat sealability is on the inner surface side as a sealant layer. One or more gas barrier layers 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, and a first base material having heat sealability. A packaging material laminate,
In the packaging material laminate, the first base material exposed on one side thereof and the second base material made of a thermoplastic resin film adjacent to the first base material are laminated without using an adhesive and an anchor coating agent. And
Either one of the adhesive surface of the first base material and the adhesive surface of the second base material is provided with a thermal adhesion modified layer by surface modification using an atmospheric pressure plasma processing apparatus, Is subjected to air corona treatment, and the first base material and the second base material are bonded by thermocompression bonding without applying an adhesive and an anchor coat agent. Packaging material laminate. One or more gas barrier layers 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, and a first base material having heat sealability. A packaging material laminate,
In the packaging material laminate, the first base material exposed on one side thereof and the second base material made of a thermoplastic resin film adjacent to the first base material are laminated without using an adhesive and an anchor coating agent. And
A thermal adhesion modified layer is formed on the adhesive surface of the first base material and the adhesive surface of the second base material by surface modification using an atmospheric pressure plasma processing apparatus, and the first base material A packaging material laminate, wherein the base material of 1 and the second base material are bonded by thermocompression bonding without applying an adhesive and an anchor coating agent.   The first substrate is unstretched polyethylene (PE) or unstretched polypropylene (CPP), and the second substrate is polyethylene terephthalate (PET), polyamide (PA), polyethylene naphthalate (PEN). , One selected from the group consisting of polyacrylonitrile (PAN), polycarbonate (PC), polyimide (PI), polyvinyl chloride (PVC), and ethylene-vinyl alcohol copolymer (EVOH) The packaging material laminate according to claim 10 or 11.   The packaging material laminate according to claim 10 or 11, wherein the second substrate is made of a thermoplastic resin film having gas barrier properties and also serves as the gas barrier layer.   14. A packaging produced by using the packaging material laminate according to claim 10 so that the first base material having heat sealability is an inner surface side as a sealant layer. body.

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