Molded packaging material and method for producing it

Abstract

A molded packaging material (1) comprising: a heat-resistant resin layer (2) as an outer layer; a polypropylene layer (3) as an inner layer; and a metal foil layer (4) arranged between the heat-resistant resin layer (2) and the polypropylene layer (3), wherein at least one inner surface (4a) of the metal foil layer (4) is subjected to a chemical conversion treatment, and wherein the polypropylene layer (3) is laminated to the chemically converted surface of an inner surface of the metal foil layer (4) by means of an adhesive layer (5), wherein the adhesive layer (5) is formed by applying an adhesive to the chemically converted surface of the inner surface of the metal foil layer (4), wherein the adhesive comprises at least an organic solvent, a polyolefin resin with a carboxyl group, which is dissolved in the organic solvent and has an MFR of 5 g / 10 min to 42 g / 10 min, measured at 130 °C.has a melting point of 50 °C to 90 °C, and contains a multifunctional isocyanate compound, wherein the polypropylene layer (3) is formed as the inner layer from a copolymer resin which contains at least propylene and ethylene as a copolymerization component, has a melting point of 135 °C to 155 °C and has a melting point frustum (MFR) of 6 g / 10 min to 25 g / 10 min, measured at 230 °C, and wherein an equivalent ratio (NCO / OH) of the isocyanate group (NCO) in the multifunctional isocyanate compound and the hydroxyl group (OH), which constitutes the carboxyl group in the polyolefin resin, is 0.1 to 9.0.

Description

TECHNICAL AREA

[0001] The present invention relates to a shaped packaging material, which is preferably used as a housing for a secondary battery for use in, for example, laptops, mobile phones, automobiles or for a stationary lithium-ion secondary battery, and which is also preferably used as a packaging material for, for example, food products or pharmaceutical products.

[0002] In this description, “a polyolefin resin with a carboxyl group” can be referred to as “a polyolefin resin which contains a carboxyl group”, and “a polypropylene resin with a carboxyl group” can be referred to as “a polypropylene resin which contains a carboxyl group”.

[0003] Furthermore, in this description, a “melting point” of a resin refers to a peak temperature (melting point) which is measured using a method specified in JIS K7121 (1987) “Transition Temperature Measuring Method of Plastic”, using a DSC (DSC = “differential scanning calorimeter”) at a temperature increase rate of 10°C / min.

[0004] Furthermore, in this description, an MFR (MFR = “melt flow rate”) of a resin is a value which is measured under the measurement condition or state of 130°C and 2.16 kg load (21.18 N) according to JIS K7210 (1999 revised version). TECHNICAL BACKGROUND

[0005] A widely known laminate packaging material uses a metal foil that has good barrier properties with respect to oxygen or moisture in order to prevent chemical changes, deterioration and corrosion, etc., of contents such as food, pharmaceutical products, etc. in the packaging material.

[0006] On the other hand, with the reduction in size and weight of various electronic devices, such as OA devices like personal computers, mobile phones, gaming devices, stereo headphones, and electronic notebooks, lithium-ion polymer secondary batteries are increasingly used as power supply units, primarily due to their size and weight reduction. In a lithium-ion polymer secondary battery, if the electrolyte reacts with water to form hydrofluoric acid, the battery's performance can deteriorate, or leakage can occur due to corrosion of the aluminum foil. Therefore, a laminate packaging material with a high sealing function and a metal foil with excellent moisture barrier properties is used as the material for the housing (receiving case) of lithium-ion polymer secondary batteries.

[0007] A laminate packaging material is used as a material for use in a housing for lithium-ion polymer secondary batteries (packaging material), in which an outer layer made of a heat-resistant resin film, an intermediate layer made of aluminum foil as a moisture barrier layer, and an inner layer made of a polyolefin film for sealing the polymer electrolytes as contents are integrally laminated.

[0008] The aforementioned laminate packaging material is formed into a three-dimensional cuboid shape, etc., by widening / bulging / protrusion or deep drawing, in order to increase the capacity for filling with as much polymer electrolyte as possible in order to create a battery casing.

[0009] The following methods are known as methods for producing the laminate packaging material.According to one of the methods, in a laminate forming an embossed outer body consisting of at least one base material layer, an adhesive layer, a chemical conversion treatment layer, an aluminum, a chemical conversion treatment layer, an acid-modified PP film layer, an extruded resin layer, and an innermost layer, both surfaces of the aluminum are subjected to a chemical conversion treatment, and the base material layer is applied / bonded to one of the surfaces of the aluminum by means of a dry lamination process. Then, an acid-modified PP is applied to the other chemical conversion treatment surface and baked onto it. Finally, the acid-modified PP surface and the innermost layer (cast PP) are laminated with an extruded resin by means of a sandwich lamination process (see patent document 1).According to the other method, in a laminate that forms an embossed outer body, which is formed from at least one base material layer, an adhesive layer, a chemical conversion layer, an aluminum layer, a chemical conversion layer, an acid-modified PP film layer, an extruded resin layer, and an innermost layer, an area of ​​the aluminum is subjected to a chemical conversion treatment, and the base material layer is applied to the chemical conversion surface by means of a dry lamination process.The aluminum is glued, then the unprocessed surface is subjected to a chemical conversion treatment, an acid-modified PP is applied to the chemical conversion surface and fired onto it, and then the acid-modified PP surface and the innermost layer (cast PP) are laminated with an extruded resin using a sandwich lamination process (see patent document 1).

[0010] Furthermore, other methods are also known. According to one of the methods, in a laminate forming an embossed outer body consisting of at least one base material layer, an adhesive layer, a chemical conversion treatment layer, aluminum, another chemical conversion treatment layer, an acid-modified PP film layer, and an innermost layer, both surfaces of which are subjected to a chemical conversion treatment, one of the chemical conversion treatment surfaces and the base material are laminated using a dry lamination process, then an acid-modified PP is applied to the other chemical conversion treatment surface and fired onto it, and then the innermost layer is laminated onto the acid-modified PP surface (see patent document 2).According to the other method, in a laminate forming an embossed outer body consisting of at least one base material layer, an adhesive layer, a chemical conversion treatment layer, an aluminum layer, a chemical conversion treatment layer, an acid-modified PP film layer, and an innermost layer, one surface of the aluminum is subjected to a chemical conversion treatment, the chemical conversion treatment surface and the base material are laminated using a dry lamination process, then the other surface of the aluminum is subjected to a chemical conversion treatment, and then an acid-modified PP is applied and fired onto it, and subsequently a cast polypropylene is laminated onto the acid-modified PP surface using a heat lamination process (see patent document 2).

[0011] Another manufacturing process is also known in which an organosol, which has an acid-modified polyolefin as a solid component, is applied to a chromium-containing chemical conversion treatment film surface of a metal foil, which is produced from a metal foil main body and a chromium-containing chemical conversion treatment film, which is formed by subjecting at least one surface of the metal foil main body to a chromate treatment, then the organosol is dried to form an adhesive film, subsequently an acid-modified polyolefin film of the same type as the acid-modified polyolefin in the organosol is pressure-bonded to the adhesive film to join the metal foil and the acid-modified polyolefin film together, thereby providing the acid-modified polyolefin film as a heat-sealable layer (see patent document 3). STATE-OF-THE-ART DOCUMENTS PATENT DOCUMENTS

[0012] Patent document 1: Japanese unexamined patent application publication number 2001-172779 Patent document 2: Japanese unexamined patent application publication number 2001-176457 Patent document 3: Japanese unexamined patent application publication number 2000-357494 SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED WITH THE INVENTION

[0013] However, in each of the above-mentioned conventional technologies, the lamination strength between the metal foil layer and the innermost layer (inner layer; sealant layer) was insufficient.

[0014] The present invention was made with regard to the aforementioned technical background and aims to provide a molded packaging material with excellent interlaminar strength, capable of preventing deterioration of interlaminar strength due to the influence of electrolytes, and also capable of preventing deterioration of interlaminar strength due to the influence of heat generation and / or expansion / contraction of a packaging material caused by repeated loading / unloading, and also aims to provide a manufacturing process capable of producing a molded packaging material with excellent interlaminar strength with high productivity. MEANS TO SOLVE THE PROBLEMS

[0015] To achieve the above-mentioned objectives, the present invention provides the following means. 1. A molded packaging material comprising: a heat-resistant resin layer as an outer layer; a polypropylene layer as an inner layer; and a metal foil layer which is arranged between the heat-resistant resin layer and the polypropylene layer, wherein at least one inner surface of the metal foil layer is subjected to a chemical conversion treatment, and wherein the polypropylene layer is laminated to the chemically converted surface of an inner surface of the metal foil layer by means of an adhesive layer, and wherein the adhesive layer is formed by applying an adhesive to the chemically transformed surface of the inside of the metal foil layer, wherein the adhesive comprises at least an organic solvent, a polyolefin resin with a carboxyl group dissolved in the organic solvent and having an MFR of 5 g / 10 min to 42 g / 10 min, measured at 130°C, and a multifunctional isocyanate compound. 2. The molded packaging material as specified in point 1 above, wherein the adhesive further comprises a polyolefin resin having a carboxyl group and a melting point of 120°C to 170°C, dispersed in the organic solvent. 3. The molded packaging material as specified in point 1 or 2 above, wherein the adhesive layer is formed by applying the adhesive to the chemically transformed surface of the inside of the metal foil layer and subsequently subjecting the applied adhesive to a firing treatment. 4. The molded packaging material as specified in point 3 above, wherein the polypropylene layer is formed by an extrusion lamination process by laminating a polypropylene layer onto an inner surface of the adhesive layer, which is formed by flame treatment. 5. The molded packaging material as specified in any one of the above points 1 to 4, wherein the polypropylene layer is formed as the inner layer from a copolymer resin which contains at least propylene and ethylene as a copolymerization component, has a melting point of 135°C to 155°C and has an MFR of 6 g / 10 min to 25 g / 10 min, measured at 230°C. 6. The molded packaging material as specified under any of the above points 1 to 5, wherein the molded packaging material is used as a battery casing. 7. The shaped packaging material as specified under any of the above points 1 to 5, wherein the shaped packaging material is used as a packaging material for food or pharmaceutical products. 8. A method for producing a molded packaging material, comprising: a step of bonding a heat-resistant resin film to a surface of a metal foil using a second adhesive; a step of forming a first adhesive layer by applying a first adhesive to the other surface of the metal foil, wherein the first adhesive contains at least an organic solvent, a polyolefin resin with a carboxyl group dissolved in the organic solvent and having an MFR of 5 g / 10 min to 42 g / 10 min, measured at 130°C, and a multifunctional isocyanate compound; and a step of laminating a polypropylene layer as an inner layer onto a non-laminated surface of the first adhesive layer, wherein the metal foil is a metal foil in which an area of ​​the metal foil, onto which at least the first adhesive is to be applied, is subjected to a chemical transformation treatment. 9. The method for producing a molded packaging material as specified in point 8 above, wherein the first adhesive further comprises a polyolefin resin having a carboxyl group and a melting point of 120°C to 170°C, dispersed in the organic solvent. 10. The method for producing a molded packaging material as specified in point 8 or 9 above, wherein, after the first adhesive has been applied, the first adhesive is heated to carry out a firing process in order to form the first adhesive layer. 11. The method for producing a molded packaging material as specified in any one of points 8 to 10 above, wherein a copolymer resin is used as the polypropylene of the inner layer, which contains at least propylene and ethylene as a copolymerization component, has a melting point of 135°C to 155°C and has an MFR of 6 g / 10 min to 25 g / 10 min, measured at 230°C. EFFECTS OF INVENTION

[0016] According to the invention as specified in paragraph (1) above, a polypropylene layer is laminated onto the chemically treated surface of the inner side of the metal foil layer, and the adhesive layer is formed by applying an adhesive to the chemically treated surface of the inner side of the metal foil layer, wherein the adhesive contains at least an organic solvent, a polyolefin resin with a carboxyl group dissolved in the organic solvent and having a melt flow rate (MFR) of 5 g / 10 min to 42 g / 10 min, measured at 130°C, and a multifunctional isocyanate compound. Therefore, sufficient interlaminar strength can be ensured.Furthermore, the adhesive has excellent affinity for both the metal foil layer and the polypropylene layer (inner layer), thus further improving the interlaminar strength between the metal foil layer and the polypropylene layer (inner layer). Therefore, when used, for example, as a battery casing, it is possible to prevent a deterioration of the interlaminar strength due to the effects of the electrolytes, and it is also possible to prevent a deterioration of the interlaminar strength due to the effects of heat generation and / or expansion / contraction of the packaging material caused by repeated charging / discharging, thus ensuring adequate sealing performance.Furthermore, since at least one surface of the metal foil layer is subjected to a chemical conversion treatment, corrosion of the surface of the metal foil by the contents (electrolytes of batteries, food products, pharmaceutical products, etc.) can be sufficiently avoided.

[0017] According to the invention as specified in point (2) above, since the adhesive further contains a polyolefin resin which has a carboxyl group and a melting point of 120°C to 170°C, in a manner dispersed in the organic solvent, the interlaminar strength, the electrolyte resistance and the sealing function / sealing performance can be further improved.

[0018] According to the invention as specified in point (3) above, since the adhesive layer is formed by applying the adhesive and subsequently subjecting the applied adhesive to a firing process, there is an advantage that it can be wound once for the next processing.

[0019] According to the invention as specified in point (4) above, since the polypropylene layer is formed using an extrusion lamination process by laminating a polypropylene onto an inner surface of the adhesive layer, which is formed by flame treatment, the interlaminar strength between the metal foil layer and the polypropylene layer (inner layer) can be further improved.

[0020] According to the invention as specified in point (5) above, since the polypropylene layer (inner layer) is formed with a copolymer resin which contains at least propylene and ethylene as a copolymerization component, has a melting point of 135°C to 155°C and has an MFR of 6 g / 10 min to 25 g / 10 min measured at 230°C, sufficient heat resistance can be ensured, suitable fluidity can be achieved at the time of sealing, and excellent sealing function can be ensured.

[0021] According to the invention as specified in point (6) above, a material for a battery casing with high interlaminar strength can be provided.

[0022] According to the invention as specified in point (7) above, a food packaging material with high interlaminar strength or a pharmaceutical product packaging material with high interlaminar strength can be provided.

[0023] According to the invention as described in point (8) above, the method comprises a step of applying a heat-resistant resin film to a surface of a metal foil by means of a second adhesive, a step of forming a first adhesive layer by applying a first adhesive to the other surface of the metal foil, wherein the first adhesive contains at least an organic solvent, a polyolefin resin with a carboxyl group dissolved in the organic solvent and having an MFR of 5 g / 10 min to 42 g / 10 min measured at 130°C, and a multifunctional isocyanate compound, and a step of laminating a polypropylene layer as an inner layer onto a non-laminated surface of the first adhesive layer, wherein the metal foil used is a metal foil in which a surface of the metal foil, onto which at least the first adhesive is to be applied,By subjecting the material to a chemical transformation treatment, a molded packaging material can be produced that is capable of ensuring sufficient interlaminar strength. Furthermore, the first adhesive layer has excellent affinity to both the metal foil layer and the polypropylene layer (inner layer), thus further improving the interlaminar strength between these layers. Therefore, when the resulting packaging material is formed, for example, into a battery casing, it is possible to prevent deterioration of the interlaminar strength due to the influence of the electrolytes, and it is also possible to prevent deterioration due to heat generation and / or expansion / contraction of the packaging material caused by repeated charging / discharging, thus ensuring adequate sealing performance. Furthermore,Since at least one surface of the metal foil layer, onto which the first adhesive is to be applied, is subjected to a chemical transformation treatment, a molded packaging material can be produced which is able to prevent corrosion of the metal foil surface by the contents (electrolyte(s) of a battery, food products, pharmaceutical products, etc.).

[0024] According to the invention as specified in point (9) above, since the first adhesive further contains a polyolifine resin which has a carboxyl group and a melting point of 120°C to 170°C, in a manner dispersed in the organic solvent, the interlaminar strength, the electrolyte resistance and the sealing function can be further improved.

[0025] According to the invention as specified in point (10) above, since the first adhesive layer is formed by applying the first adhesive and subsequently heating it in order to thermally treat or burn the first adhesive, there is an advantage that it can be wound up once for the next processing.

[0026] According to the invention as specified in point (11) above, a copolymer resin is used as a polypropylene (inner layer) which contains at least propylene and ethylene as a copolymerization component, has a melting point of 135°C to 155°C and has a MFR of 6 g / 10 min to 25 g / 10 min, measured at 230°C, and therefore a molded packaging material with sufficient heat resistance can be produced which is able to achieve suitable fluidity at the time of sealing and to ensure an excellent sealing function. BRIEF DESCRIPTION OF THE DRAWING

[0027] Fig. Figure 1 is a cross-sectional view showing an embodiment of a molded packaging material according to the present invention.

[0028] Fig. Figure 2 is a side view showing an example of a manufacturing process for a molded packaging material according to the present invention.

[0029] Fig. Figure 3 is a cross-sectional view showing another embodiment of a molded packaging material according to the present invention.

[0030] Fig. Figure 4 is a side view showing another example of a manufacturing process for a molded packaging material according to the present invention. EXECUTIONAL FORMS FOR IMPLEMENTING THE INVENTION

[0031] An embodiment of a molded packaging material 1 According to the present invention, in Fig. 1 shown. This molded packaging material1 It is, for example, shaped into an approximate rectangular parallelepiped shape with an open top surface, and is used as a casing for lithium-ion polymer secondary batteries.

[0032] In the molded packaging material 1 is a heat-resistant or heat-resistant resin layer (outer layer) 2 integrally laminated onto one of the surfaces with a metal foil layer 4 by means of a second adhesive layer 11 , and a polypropylene layer (inner layer) 3 is integrally laminated to the other surface of the metal foil layer 4 by means of a first adhesive layer 5 .

[0033] At least the inner surface 4a the metal foil layer 4 (Area on the side of the polypropylene layer 3 ) undergoes a chemical transformation treatment, and the first adhesive layer 5is on the chemical conversion treatment area 4a on the inner surface of the metal foil layer 4 laminated.

[0034] The first adhesive layer 5 is formed by applying a first adhesive to the chemical conversion treatment surface 4a on the inside of the metal foil layer 4 The first adhesive contains: (A) an organic solvent; (B) a polyolefin resin with a carboxyl group dissolved in the organic solvent and having an MFR (melt flow rate) of 5 g / 10 min to 42 g / 10 min, measured at 130°C; and (C) a multifunctional isocyanate compound.

[0035] In this embodiment, the first adhesive layer 5 formed by applying the first adhesive to the chemical conversion treatment surface 4a on the inner surface of the metal foil layer4 , whereby the applied adhesive is subsequently subjected to a firing treatment.

[0036] Furthermore, in this embodiment the polypropylene layer (inner layer) 3 formed by laminating polypropylene onto the inner surface 5a the first adhesive layer 5 , which is formed by burning, using an extrusion lamination process.

[0037] In the molded packaging material 1 The above structure includes a polypropylene layer 3 to the chemical conversion treatment area 4a on the metal foil layer 4 by means of an adhesive layer 5 laminated, and the first adhesive layer 5 is formed by applying a first adhesive to the chemical conversion treatment surface 4aon the inside of the metal foil layer, wherein the adhesive contains at least an organic solvent, a polyolefin resin with a carboxyl group dissolved in the organic solvent and having an MFR of 5 g / 10 min to 42 g / 10 min, measured at 130°C, and a multifunctional isocyanate compound, and the first adhesive has an excellent affinity for the metal foil layer 4 and the polypropylene layer (inner layer) 3 Therefore, the interlaminar strength between the metal foil layer can be increased. 4 and the polypropylene layer (inner layer) 3 to be sufficiently / appropriately improved. For this reason, if the packaging material 1For example, if it is molded into a battery casing, it is possible to avoid a deterioration of the interlaminar strength due to the influence of electrolytes, and it is also possible to avoid a deterioration of the interlaminar strength due to the influence of heat generation and / or expansion / contraction of the packaging material caused by repeated charging / discharging, which ensures a sufficient sealing function.

[0038] Next, an example of a process for manufacturing a molded packaging material will be presented. 1 according to the present invention with reference to Fig. 2 described. First, a heat-resistant stretched resin film (heat-resistant resin layer) is applied. 2 on a surface of the metal foil 4 with a second adhesive 11applied / glued on (adhesion step). For example, the adhesion step is carried out using a dry lamination process. When the metal foil 4 A metal foil is used, in which at least the inner surface 4a (The area on one side, to which the first adhesive used in the next step is applied) undergoes a chemical transformation treatment. This can involve a metal foil. 4 to be used, where both surfaces have been / are undergoing a chemical transformation treatment.

[0039] On the other surface 4a (Inner surface) of the metal foil 4 A first adhesive agent is applied and then dried to form a first layer of adhesive. 5 to form. The first adhesive contains at least: (A) an organic solvent; (B) a polyolefin resin with a carboxyl group dissolved in the organic solvent and having an MFR (melt flow rate) of 5 g / 10 min to 42 g / 10 min, measured at 130°C; (C) a multifunctional isocyanate compound.

[0040] It is preferred that the first adhesive layer 5 The material is formed by applying the first adhesive and then applying heat to perform a firing process (firing-processing step). A laminate 30 is obtained in this way (see Fig. 2).

[0041] The method for applying the first adhesive (processing solution) is not limited to a specific one, but, for example, an engraving roller method can be cited as an example.

[0042] It is preferred that the heating temperature for the curing treatment be set between 80°C and 250°C. Setting / fixing the temperature at 80°C or higher can improve the adhesion of the first adhesion layer. 5 regarding the metal foil 4 Sufficient / appropriate assurance is provided, and by setting / fixing the temperature at 250°C or less, the deterioration of the first adhesive layer can be prevented. 5 be controlled / restricted.

[0043] Next, a polypropylene layer will be applied. 3 on a non-laminated surface 5a the first adhesive layer 5 from the laminate 30 laminated using an extrusion lamination process (extrusion lamination step). At the time of extrusion lamination, as in Fig. 2 shown, the laminate 30 and the extruded polypropylene 3X using a rubber roller 21 and a cooling roller 22 pressed (see Fig. 2) to thereby create a shaped packaging material 1 the present invention, as it is described in Fig. As shown in 1, to obtain.

[0044] The material of the surface of the cooling roller 22 is not limited to a specific material, but commonly used materials such as stainless steel, etc., can be used.

[0045] The heat-resistant resin layer (outer layer) 2 is not limited to a specific one, but examples include nylon film / sheet, polyester film / sheet, etc., and preferably stretched films / sheets thereof are used. Furthermore, it is particularly preferred that the heat-resistant resin layer be made of 2to use a biaxially oriented nylon film, a biaxially oriented polybutylene terephthalate (PBT) film, a biaxially oriented polyethylene terephthalate (PET) film, or a biaxially oriented polyethylene naphthalate (PEN) film. The nylon film is not specifically restricted, but examples include a nylon 6 film, a nylon 6.6 film, an MXD nylon film, etc. Furthermore, the heat-resistant resin layer can be... 2 be formed from a single layer or a multi-layer arrangement, e.g. made from PET film / nylon film.

[0046] It is preferred that the thickness of the heat-resistant resin layer 2The thickness is 12 μm to 50 μm. If a polyester film is used, it is preferred that the thickness be 12 μm to 50 μm, and if a nylon film is used, it is preferred that the thickness be 15 μm to 50 μm. By setting / fixing the thickness to the appropriate lower limit or more, sufficient strength for a packaging material can be ensured, and by setting / fixing the thickness to the appropriate upper limit or less, the stress at the time of warping / bulging or stretching can be reduced, thereby improving formability.

[0047] The metal foil layer 4 Its function is to provide gas barrier properties to prevent the ingress of oxygen and / or moisture into the molded packaging material. 1 The metal foil layer 4is not limited to a specific type, but examples include aluminum foil, copper foil, etc., and aluminum foil is most commonly used. It is preferred that the thickness of the metal foil layer be 4 The thickness ranges from 20 μm to 100 μm. By setting / fixing the thickness to 20 μm or more, the formation of pinholes during the rolling process in the production of the metal foil can be avoided, and by setting / fixing the thickness to 100 μm or less, the stress during the buckling or drawing process can be reduced, thereby improving formability.

[0048] In the metal foil layer 4 at least the inner surface will be / is 4a (Area on the side of the first adhesive layer 5) undergoes a chemical conversion treatment. By subjecting it to such a chemical conversion treatment, corrosion of the metal foil surface by its contents (electrolytes from batteries, food products, pharmaceutical products, etc.) can be sufficiently / effectively prevented. For example, the metal foil undergoes a chemical conversion treatment through the following process. That is to say, for example, on a surface of a metal foil that has undergone a reduction treatment, 1) an aqueous solution of a mixture of phosphoric acid, chromic acid and a fluoride metal salt; 2) an aqueous solution of a mixture of phosphoric acid, chromic acid and a metal salt and a non-metal salt of fluoride; and 3) an aqueous solution of a mixture of an acrylic resin and / or a phenolic resin, phosphoric acid, chromic acid and a fluoride metal salt It is applied / applied, and then dried to perform a chemical conversion treatment.

[0049] The first adhesive layer 5 is a film (coating film) that is formed by applying a first adhesive (processing solution) to the chemical conversion treatment surface on the inside of the metal foil layer. 4 and subsequent drying of the same. The first adhesive contains: (A) an organic solvent; (B) a polyolefin resin with a carboxyl group, dissolved in the organic solvent and having a melt flow rate (MFR) of 5 g / 10 min to 42 g / 10 min, measured at 130°C; and (C) a multifunctional isocyanate compound.

[0050] It is preferred that the film (coating film) is formed by carrying out a firing treatment by heating after the first adhesion promoter (process solution) has been applied.

[0051] Furthermore, it is preferred that the first adhesive (process solution) has a composition which contains (D) a polyolefin resin with a carboxyl group, which is dispersed / divided in the organic solvent and has a melting point of 120°C to 170°C.

[0052] It is preferred that the organic solvent (A component) forming the first adhesive (process solution) is an organic solvent that is easily evaporated and removed, for example, by heating the adhesive composition. Examples of such organic solvents include aromatic organic solvents such as toluene, xylene, etc.; aliphatic organic solvents such as n-hexane, etc.; alicyclic organic solvents such as cyclohexane, methylcyclohexane, etc.; ketone-based organic solvents such as methyl ethyl ketone, etc.; and alcohol-based organic solvents such as ethanol, isopropyl alcohol, etc. Only one type of such organic solvent may be used, or two or more types may be combined.

[0053] Furthermore, it is possible that the organic solvent (component A) has a composition that includes at least one alcohol-based organic solvent (ethanol, isopropyl alcohol, etc.), in which case the storage stability of the adhesive can be improved. It is also preferred that the proportion of the alcohol-based organic solvent in the total amount of the organic solvent is set / fixed to 0.1 wt% to 20 wt%, and it is particularly preferred that the proportion is set / fixed to 0.3 wt% to 10 wt%.

[0054] Examples of polyolefin resins (B-component, D-component) with a carboxyl group include polyolefins modified with an unsaturated carboxylic acid and / or a derivative thereof, etc.

[0055] An example of such a modification is a graft addition modification.

[0056] Unsaturated carboxylic acids and their derivatives are not specifically restricted, but examples include acrylic acid, methacrylic acid, maleic anhydride, maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid, 5-norbornene-2,3-dicarboxylic acid, etc. Only one type of such an unsaturated carboxylic acid can be used, or two or more types can be combined.

[0057] It is preferred to use polypropylene which is graft-addition modified with at least one type of compound selected from the group consisting of maleic anhydride, maleic acid, fumaric acid, acrylic acid and methacrylic acid, and polypropylene which is graft-addition modified by maleic anhydride is particularly suitable.

[0058] The process for producing the polyolefin resin (B component, D component) with a carboxyl group is not specifically restricted, but examples include a solution process in which polypropylene is dissolved in an organic solvent and reacts with carboxylic acid (maleic anhydride, etc.) in the presence of a radical generator, and a fusion process in which polypropylene is heated and melted to react with carboxylic acid (maleic anhydride, etc.) in the presence of a radical generator, etc.

[0059] For the aforementioned B component and the D component, in general, when the average molecular weight (weight-mean molecular weight, etc.) of the polyolefin resin with a carboxyl group decreases, the MFR increases, and when the average molecular weight (weight-mean molecular weight, etc.) of the polyolefin resin with a carboxyl group increases, the MFR decreases.

[0060] For the B component mentioned above, if the MFR, measured at 130°C, is lower than 5 g / 10 min, the interlaminar strength decreases and the electrolyte resistance becomes poor, and if the MFR, measured at 130°C, exceeds 42 g / 10 min, the interlaminar strength decreases and the electrolyte resistance deteriorates.

[0061] The carboxyl group content in the aforementioned B component, from the point of view of improving adhesion properties, is preferably 0.10 mmol to 2.0 mmol per 1 g of polyolefin resin, and particularly preferably 0.15 mmol to 1.0 mmol. If the carboxyl group content is within the aforementioned suitable range, greater lamination strength can be ensured.

[0062] The melting point of the aforementioned D component is preferably 50°C to 90°C, more preferably 60°C to 85°C. If the melting point is within the aforementioned suitable range, high lamination strength can be ensured even at high temperatures.

[0063] The melting point of the aforementioned D component is 120°C to 170°C, preferably 130°C to 160°C. If such a D component (polyolefin resin with a carboxyl group having a melting point of 120°C to 170°C) is included, the interlaminar strength can be improved at a high temperature of approximately 80°C. On the other hand, if the melting point exceeds 170°C, defects may occur in the laminate, and the adhesion temperature at the time of adhesion must be set higher, which may reduce productivity.

[0064] The carboxyl group content in the aforementioned D-component, from the perspective of improving adhesion, is preferably 0.01 mmol to 2 mmol per 1 g of polyolefin resin, more preferably 0.1 mmol to 1.0 mmol. If the carboxyl group content is within the aforementioned suitable range, greater lamination strength can be ensured.

[0065] The multifunctional isocyanate compound is not specifically restricted as long as two or more isocyanate groups are present in a single molecule, and various types of isocyanate compounds can be used, such as aromatic, aliphatic, and alicyclic isocyanates, as well as modified versions of these isocyanates. Examples include diisocyanate compounds such as toluene diisocyanate (TDI), diphenylmethane diisocyanate, hexamethylene diisocyanate (HDI), isophorone diisocyanate, etc., and a modified version in which these compounds are isocyanurate-modified, burette-modified, or adduct-modified with a polyhydric alcohol, such as trimethylolpropane, etc., and a block-type isocyanate in which the isocyanate is masked and stabilized with a blocking agent, etc. It is preferred to use a compound containing three or more isocyanate groups in a single molecule.Only one type of multifunctional isocyanate compound can be used, or two or more types can be combined. Furthermore, in the first adhesive (process solution), the multifunctional isocyanate compound is typically dissolved in an organic solvent.

[0066] The ratio of the polyolefin resin containing a carboxyl group (component B, component D) in the first adhesion promoter (process solution) and the multifunctional isocyanate compound is not specifically restricted, but it is preferred that the equivalent ratio (NCO / OH) of the isocyanate group (NCO) in the multifunctional isocyanate compound and the hydroxyl group (OH) constituting the carboxyl group in the polyolefin resin (component B and component D) be between 0.01 and 12.0. If the equivalent ratio (NCO / OH) is between 0.01 and 12.0, a first adhesion promoter composition with particularly excellent initial adhesion properties can be provided, and a cured material (first adhesion promoter layer) with sufficient crosslinking density and flexibility, etc., can be formed. The equivalent ratio (NCO / OH) is preferably 0.04 to 12.0, more preferably 0.1 to 12.0, and even more preferably 0.1 to 9.0.Furthermore, if only the B component is present as a polyolefin resin with a carboxyl group, an equivalent ratio is = (NCO) / (OH of the B component), and if the B component and the D component are present as a polyolefin resin with a carboxyl group, an equivalent ratio is = (NCO) / (OH of the B component + OH of the D component).

[0067] In the case where component D is included, the mass-weight ratio of component B and component D in the first adhesive (process solution) is preferably set as follows, assuming the sum of both is 100 wt%. It is preferred that component B is 1 wt% to 70 wt% and component D is 99 wt% to 30 wt%; more preferably, component B is 3 wt% to 50 wt% and component D is 97 wt% to 50 wt%; and most preferably, component B is 5 wt% to 40 wt% and component D is 95 wt% to 60 wt%. Within the aforementioned preferred range, high lamination strength can be achieved at room temperature (25°C) and elevated temperatures.

[0068] It is preferred that the training quantity of the first adhesive layer (film) 5 , which is shaped / formed by the firing process, is set / fixed to 0.5 g / m² 2 up to 5.0 g / m² 2Solids content. By adjusting to 0.5 g / m³ 2 or more, sufficient adhesion can be achieved, and by adjusting to 5.0 g / m² 2 If the amount of solvent is less than the amount used, the drying time can be shortened, and it is possible to improve process efficiency and avoid the solvent leaching into the packaging material. 1 remains, and furthermore, it is possible to improve the moisture barrier properties.

[0069] The resin, which forms the polypropylene layer (inner layer) (sealant layer) 3 The scope of education is not specifically limited, but examples include: 1) a random copolymer resin or statistical copolymer resin containing propylene and ethylene as a copolymerization component, 2) a copolymer resin containing propylene, ethylene and butene as a copolymerization component, and 3) a block copolymer resin containing propylene and ethylene as a copolymerization component, etc.

[0070] An olefin-based thermoplastic elastomer can be mixed into the aforementioned 1) to 3) copolymer resins.

[0071] As the resin which forms the polypropylene layer (inner layer) 3When forming a copolymer resin, it is preferred to use one that contains at least propylene and ethylene as copolymerization components and has a melting point of 135°C to 155°C. A copolymer resin with a melting point of 135°C to 155°C is defined as a resin with a peak temperature (melting point) of 135°C to 155°C, measured using a differential scan calorimeter (DSC) at a temperature increase rate of 10°C / min. If the melting point is 135°C or higher, sufficient heat resistance can be ensured, and if the melting point is 155°C or lower, good sealing performance can be guaranteed.

[0072] As a resin which forms the polypropylene layer (inner layer) 3When forming a seal, it is preferred to use a copolymer resin containing at least propylene and ethylene as copolymerization components and having a minimum flow rate (MFR) of 6 g / 10 min to 25 g / 10 min, measured at 230°C. If the MFR is 6 g / 10 min or more, extrusion lamination can be easily carried out, and if the MFR is 25 g / 10 min or less, the resin's fluidity at the time of sealing / caking is adequate, thus ensuring an even better sealing performance.

[0073] It is preferred that the thickness of the polypropylene layer be between 13 μm and 80 μm. If it is 10 μm or more, sufficient sealing strength can be achieved, and if it is 80 μm or less, loss of the moisture barrier from the end surface can be adequately prevented. The polypropylene layer 3It can be formed as a single layer or a multi-layer arrangement, which is formed by co-extrusion of polypropylene or double extrusion lamination of polypropylene. In the latter case, for example, by placing a polypropylene layer with high fluidity on the outer side (side of the innermost layer) of the polypropylene layer with low fluidity, it is possible to sufficiently prevent the seal thickness from becoming extremely thin due to irregular flow of the polypropylene layers during the sealing process.

[0074] The adhesive, which forms the second adhesive layer 11The composition of the adhesive is not specifically restricted, but a two-part, curing-type urethane-based adhesive, etc., containing, for example, a polyol component and an isocyanate component, can be cited as an example. This two-part, curing-type urethane-based adhesive is particularly suitable for use with a dry lamination process at the time of adhesion. The composition of the polyol is not specifically restricted, but, for example, polyester polyol, polyether polyol, etc., can be cited as examples. The isocyanate compound is not specifically restricted, but, for example, a diisocyanate group such as TDI (toluene diisocyanate), HDI (hexamethylene diisocyanate), or MDI (methylenebis(4,1-phenyl) diisocyanate) can be cited as examples. It is preferred that the thickness of the second adhesive layer be 11 2 μm to 5 μm, and in particular it is especially preferred that it is 3 μm to 4 μm.

[0075] If it is within a range that does not impair the effects of the present invention, an antiblocking agent from inorganic and organic systems and an amide-based lubricant can be added to the inner layer.

[0076] By shaping (bulging, deep drawing, etc.) the molded packaging material 1 According to the present invention, various shapes, such as a cuboid shape with a high profile, etc., can be used to obtain battery housings, packaging materials for food products, and packaging materials for pharmaceutical products. In the case of the battery housings, food packaging materials, and pharmaceutical product packaging materials obtained by such shaping, it is prevented from leaking between the metal foil layers. 4 and the first adhesive layer 5For example, it is possible for a battery casing to avoid a deterioration of the lamination strength due to the influence of electrolytes, and it is also possible to avoid a deterioration of the lamination strength due to heat generation and expansion / contraction of the packaging material caused by repeated charging / discharging, thus ensuring a sufficient sealing function. EXAMPLES

[0077] Next, specific examples of the present invention will be described, but it should be understood that the present invention is not limited to these examples. <ausgangsstoffe>(Plastic example 1) Polypropylene resin J, containing a carboxyl group

[0078] Using a twin-screw extruder in which the maximum temperature of the cylinder section was set to 170°C, 100 parts by mass of a statistical propylene-ethylene copolymer (MFR: 10 g / 10 min, melting point: 85°C; hereinafter referred to as "a statistical propylene-based copolymer A"), which was prepared from 97 mol% propylene unit and 3 mol% ethylene unit and was generated using a metallocene catalyst as a polymerization catalyst, were mixed and reacted with two parts by mass of a maleic anhydride, one part by mass of lauryl methacrylate, and 1.5 parts by mass of di-t-butyl peroxide. The mixture was then degassed in the extruder under reduced pressure, and the remaining unreacted material was removed to synthesize a polypropylene resin J containing a carboxyl group (component B).In the polypropylene resin J, which contains a carboxyl group, the MFR measured at 130°C was 12 g / 10 min, and the content of the carboxyl group was 0.4 mmol per 1 g of the polypropylene resin (resin J) containing a carboxyl group. (Plastic example 2) Polypropylene resin K, containing a carboxyl group

[0079] A polypropylene resin K containing a carboxyl group (component B) was synthesized in the same manner as in plastic example 1, except that instead of the propylene-based statistical copolymer A, a statistical propylene-ethylene copolymer B (MFR: 5 g / 10 min) was used, which was prepared from 97 mol% propylene unit and 3 mol% ethylene unit and produced using a metallocene catalyst as a polymerization catalyst. In the polypropylene resin K containing a carboxyl group, the MFR, measured at 130°C, was 8 g / 10 min, and the carboxyl group content was 0.4 mmol per 1 g of the polypropylene resin (resin K) containing a carboxyl group. (Plastic example 3) Polypropylene resin L, containing a carboxyl group

[0080] A polypropylene resin L containing a carboxyl group (component B) was synthesized in the same manner as in plastic example 1, except that instead of the propylene-based statistical copolymer A, a statistical propylene-ethylene copolymer C (MFR: 36 g / 10 min) was used, which was prepared from 97 mol% propylene unit and 3 mol% ethylene unit and produced using a metallocene catalyst as a polymerization catalyst. For the polypropylene resin L containing a carboxyl group, the MFR, measured at 130°C, was 40 g / 10 min, and the carboxyl group content was 0.4 mmol per 1 g of the polypropylene resin (resin K) containing a carboxyl group. (Plastic example 4) Polypropylene resin X, containing a carboxyl group

[0081] A polypropylene resin X containing a carboxyl group (component B) was synthesized in the same manner as in plastic example 1, except that instead of the propylene-based statistical copolymer A, a statistical propylene-ethylene copolymer D (MFR: 1 g / 10 min) was used, which was prepared from 97 mol% propylene unit and 3 mol% ethylene unit and produced using a metallocene catalyst as a polymerization catalyst. For the polypropylene resin X containing a carboxyl group, the MFR, measured at 130°C, was 3 g / 10 min, and the carboxyl group content was 0.4 mmol per 1 g of the polypropylene resin (resin X) containing a carboxyl group. (Plastic example 5) Polypropylene resin Y, containing a carboxyl group

[0082] A polypropylene resin Y containing a carboxyl group (component B) was synthesized in the same manner as in plastic example 1, except that instead of the propylene-based statistical copolymer A, a statistical propylene-ethylene copolymer E (MFR: 42 g / 10 min) was used, which was prepared from 97 mol% propylene unit and 3 mol% ethylene unit and produced using a metallocene catalyst as a polymerization catalyst. For the polypropylene resin Y containing a carboxyl group, the MFR, measured at 130°C, was 45 g / 10 min, and the carboxyl group content was 0.4 mmol per 1 g of the polypropylene resin (resin Y) containing a carboxyl group. (Plastic example 6) Polypropylene resin M, containing a carboxyl group

[0083] 100 parts by mass of propylene polymer (melting point: 163°C) and 435 parts by mass of toluene were placed in an autoclave with an internal capacity of 1.5 L and equipped with a stirring device. The propylene polymer was completely melted by raising the temperature to 140°C while stirring. While the solution was maintained at 140°C, 16 parts by mass of maleic anhydride and 1.5 parts by mass of dicumyl peroxide were each added simultaneously for 4 hours while stirring. After the addition, stirring continued for one hour at 140°C to allow a post-reaction to occur, resulting in a modified polymer. Next, the solution containing the modified polymer was cooled to room temperature, and acetone was added to precipitate the modified polymer. After repeated washing of the precipitated modified polymer with acetone, it was dried to collect the modified polymer.For the modified polymer, the graft amount of maleic anhydride in the modified polymer was 2.8% by mass, the melting point was 156°C, and the content of the carboxyl group was 0.6 mmol per 1 g of the modified polymer.

[0084] Next, 15 parts by mass of the obtained modified polymer and 85 parts by mass of toluene were placed in an autoclave equipped with a stirring device, and the modified polymer was completely melted by heating to 130°C. Subsequently, after reducing the temperature to 90°C at a cooling rate of 25°C / h while stirring, it was cooled to 60°C at a cooling rate of 5°C / h. The temperature was then further reduced to 30°C at a cooling rate of 20°C / h to obtain a homogeneous, milky-white dispersion P with a 15 wt% solids content (polypropylene resin M containing a carboxyl group). The melting point of the polypropylene resin M containing a carboxyl group (component D) was 156°C, as measured by DSC. (Plastic example 7) Polypropylene resin N, which does not contain a carboxyl group

[0085] 15 parts by mass of statistical propylene-ethylene copolymer F (MFR: 12 g / 10 min), which was prepared from 97 mol% propylene unit and 3 mol% ethylene unit and produced using a metallocene catalyst as a polymerization catalyst, and 85 parts by mass of toluene were placed in an autoclave equipped with a stirrer and heated to 130°C while stirring to completely melt the copolymer F. Subsequently, after reducing the temperature to 90°C at a cooling rate of 25°C / h while stirring, it was cooled to 60°C at a cooling rate of 5°C / h. Next, the temperature was reduced to 30°C at a cooling rate of 20°C / h to obtain a uniform milky-white dispersion liquid Q with a solids content of 15 wt% (polypropylene resin N, which does not contain a carboxyl group).

[0086] Next, examples 1 to 8 and comparative examples 1 to 4 will be explained. <Beispiel 1>

[0087] A first adhesive E (processing solution) was prepared by mixing 850 g of toluene (organic solvent: component A), 150 g of polypropylene resin J containing a carboxyl group (component B), with a melt flow rate (MFR) of 12 g / 10 min measured at 130°C, and 15 g of HDI (multifunctional isocyanate compound: component C). The solids content of the first adhesive E was 15 wt%. Furthermore, component B (polypropylene resin containing a carboxyl group) was dissolved in the toluene of the solvent in the first adhesive E.

[0088] On both surfaces of an aluminum foil 4 A chemical conversion treatment solution comprising polyacrylic acid, a trivalent chromium compound, water, and alcohol was applied to a thickness of 40 µm and dried at 180°C, resulting in a chromium-containing adhesion amount of 10 mg / m². 2 was, and then a biaxially stretched polyamide film (biaxially stretched nylon film) (heat-resistant resin layer) was applied. 2 with a thickness of 25 μm using a two-part curing-type urethane-based adhesive. 11 on a surface of the aluminum foil 4 Dry lamination. After the first adhesive E (processing solution) is applied to the other surface. 4a the aluminum foil 4 Applied using an engraving roller process, it was then subjected to heating in a hot air drying oven at 200°C to create a first adhesive layer. 5 with an adhesion quantity of 2 g / m² 2 to shape and laminate 30 to obtain. Next, as in Fig. Figure 2 shows a propylene-ethylene copolymer resin (the melting point measured by DSC was 140°C and the MFR measured at 230°C was 21 g / 10 min) 3X , which comes from an extrusion die 20 when an extruder was extruded, integrally laminated onto a non-laminated surface (the surface onto which nothing was laminated) 5a the first adhesive layer 5 with a thickness of 40 μm, to create a molded packaging material 1 to obtain, as it is in Fig. 1 is shown. <Beispiel 2>

[0089] A molded packaging material 1 , as it is in Fig. The solution shown in Figure 1 was obtained in the same manner as in Example 1, except that instead of the first adhesive E, a first adhesive F (processing solution) was used, in which 170 g of toluene (organic solvent: component A), 30 g of polypropylene resin J (component B), which contains a carboxyl group and in which the MFR measured at 130°C was 12 g / 10 min, 15 g of HDI (multifunctional isocyanate compound: component C), and 800 g of the milky-white dispersion liquid P, which was obtained in plastic example 6 (680 g toluene and 120 g of polypropylene resin M, containing a carboxyl group), were composed / mixed, and that the thickness of the extruded propylene-ethylene copolymer resin 3X was set to 80 μm.

[0090] Furthermore, in example 2, the solids content in the first adhesive F was 15 wt%. In the first adhesive F (processing solution), the B component was dissolved in toluene as a solvent, but the D component (polypropylene resin M, containing a carboxyl group) was not dissolved in toluene, but dispersed in toluene. <Beispiel 3>

[0091] A molded packaging material 1 , as it is in Fig. The product shown in Figure 1 was obtained in the same manner as in Example 1, except that instead of a propylene-ethylene copolymer resin (the melting point measured by DSC was 140°C, and the MFR measured at 230°C was 21 g / 10 min), the extruded resin was obtained using a propylene-ethylene copolymer resin. 3X a propylene ethylene copolymer resin was used (the melting point measured by DSC was 155°C and the MFR measured at 230°C was 22 g / 10 min). <Beispiel 4>

[0092] A molded packaging material 1 , as it is in Fig. The product shown in Figure 1 was obtained in the same way as in Example 1, except that instead of a propylene-ethylene copolymer resin (the melting point measured by DSC was 140°C, and the MFR measured at 230°C was 21 g / 10 min), the extruded resin was obtained using a different method. 3X a propylene ethylene copolymer resin was used (the melting point measured by DSC was 155°C and the MFR measured at 230°C was 25 g / 10 min). <Beispiel 5>

[0093] A molded packaging material 1 , as it is in Fig. The B component shown in Figure 1 was obtained in the same manner as in Example 1, except that instead of a polypropylene resin J containing a carboxyl group and having an MFR of 12 g / 10 min, measured at 130°C, a polypropylene resin K containing a carboxyl group and having an MFR of 8 g / 10 min, measured at 130°C, was used. In the first adhesive used in Example 5, the polypropylene resin K containing a carboxyl group was dissolved in the toluene of the solvent. <Beispiel 6>

[0094] A molded packaging material 1 , as it is in Fig. The compound shown in Figure 1 was obtained in the same manner as in Example 1, except that instead of the polypropylene resin J, which contains a carboxyl group and has an MFR of 12 g / 10 min measured at 130°C, component B, a polypropylene resin L, which contains a carboxyl group and has an MFR of 40 g / 10 min measured at 130°C, was used. In the first adhesive used in Example 6, the polypropylene resin L, which contains a carboxyl group, was dissolved in the toluene of the solvent. <Beispiel 7>

[0095] On both surfaces of an aluminum foil 4 A chemical conversion treatment solution, made from polyacrylic acid, a trivalent chromium compound, water and alcohol, was applied to a thickness of 40 μm and dried at 180°C, resulting in a chromium-containing adhesion amount of 10 mg / m². 2 was. Subsequently, a biaxially oriented polyamide film (biaxially oriented nylon film) (heat-resistant resin layer) was applied. 2 with a thickness of 25 µm on one of the surfaces of the aluminum foil 4 using a two-part, curing-type urethane-based adhesive 11 dry lamination. Then the first adhesive E (processing solution), which was used in the example 1 mentioned above, was applied to the other surface. 4a the aluminum foil 4 applied using an engraving roller process, and then subjected to firing by heating in a hot air drying oven at 200°C to create a first adhesive layer. 5 with an adhesive quantity of 2 g / m² 2 to shape and laminate 30 to obtain. Next, as in Fig. Figure 4 shows a propylene-ethylene statistical copolymer film (the melting point measured by DSC was 140°C and the thickness was 60 μm) 3 integrally laminated using a sandwich lamination process onto a non-laminated surface (the surface onto which nothing was laminated) 5a the first adhesive layer 5 using an extruded polypropylene resin 12 , which comes from an extrusion die 20 when an extruder was used to extrude a molded packaging material 1 , as it is in Fig. As shown in 1, to obtain. <Beispiel 8>

[0096] On both surfaces of an aluminum foil 4 A chemical conversion treatment solution, made from polyacrylic acid, trivalent chromium compound, water and alcohol, was applied to a thickness of 40 μm and dried at 180°C, resulting in a chromium-containing adhesion amount of 10 mg / m². 2 was. Subsequently, a biaxially oriented polyamide film (biaxially oriented nylon film) (heat-resistant resin layer) was applied. 2 with a thickness of 25 μm on one of the surfaces of the aluminum foil 4 using a two-part, curing-type urethane-based adhesive 11 dry lamination. Subsequently, the first adhesive E (processing solution), which was used in the previously mentioned Example 1, was applied to the other surface. 4a the aluminum foil 4 Applied using an engraving roller process, it was then subjected to firing by heating in a hot air drying oven at 200°C to create a first adhesive layer. 5 with an adhesion quantity of 2 g / m² 2 to shape and laminate 30 to obtain. Next, a propylene-ethylene statistical copolymer film (the melting point measured by DSC was 140°C and the thickness is 40 μm) was integrally laminated onto a non-laminated surface (the surface onto which nothing was laminated). 5a the first adhesive layer 5 by means of a heat lamination process (the heat-resistant resin layer surface was pressed by and between a pair of heating rollers, in such a way that it contacted the heating roller at 165°C) to create a molded packaging material 1 , as it is in Fig. As shown in 1, to obtain. <Beispiel 9>

[0097] A molded packaging material 1 , as it is in Fig. The compound shown in Figure 1 was obtained in the same manner as in Example 1, except that instead of a first adhesive E, a first adhesive P was used, in which 846 g of toluene (organic solvent: component A), 4 g of isopropyl alcohol (organic solvent: component A), 150 g of polypropylene resin J containing a carboxyl group (component B) and having an MFR of 12 g / 10 min, measured at 130°C, and 15 g of HDI (multifunctional isocyanate compound: component C) were mixed. Furthermore, the solids content of the first adhesive P was 15 wt%. Additionally, component B (the polypropylene resin containing a carboxyl group) was dissolved in the organic solvent in the first adhesive P. <Beispiel 10>

[0098] A molded packaging material 1 , as it is in Fig. The solution shown in Figure 1 was obtained in the same manner as in Example 1, except that instead of a first adhesive E, a first adhesive Q was used, in which 842 g of toluene (organic solvent: component A), 8 g of isopropyl alcohol (organic solvent: component A), 150 g of polypropylene resin K containing a carboxyl group (component B) and having an MFR of 8 g / 10 min, measured at 130°C, and 15 g of HDI (multifunctional isocyanate compound: component C) were mixed. The solids content in the first adhesive Q was 15 wt%. Furthermore, component B (the polypropylene resin containing a carboxyl group) was dissolved in the organic solvent in the first adhesive Q. <Vergleichsbeispiel 1>

[0099] A molded packaging material 1 , as it is in Fig. The result shown in 1 was obtained in the same way as in Example 1, except that instead of the first adhesive E, a two-part curing-type urethane-based first adhesive Z was used, which contains a polyol component and an isocyanate component. <Vergleichsbeispiel 2>

[0100] A molded packaging material, as used in Fig. The solution shown in Figure 1 was obtained in the same manner as in Example 1, except that instead of a first adhesive E, a first adhesive W was used in which 1,000 g of the milky-white dispersion Q obtained in the plastic example 7 (850 g toluene and 150 g polypropylene resin N, which does not contain a carboxyl group) and 15 g HDI (multifunctional isocyanate compound: C component) were mixed. Furthermore, in the first adhesive W, the polypropylene resin N, which does not contain a carboxyl group, was dispersed in the toluene without being dissolved in it. <Vergleichsbeispiel 3>

[0101] A molded packaging material 1 , as it is in Fig. The B component shown in Figure 1 was obtained in the same way as in Example 1, except that instead of the polypropylene resin J, which contains a carboxyl group and has an MFR of 12 g / 10 min measured at 130°C, a polypropylene resin X, which contains a carboxyl group and has an MFR of 3 g / 10 min measured at 130°C, was used. <Vergleichsbeispiel 4>

[0102] A molded packaging material 1 , as it is in Fig. The B component shown in Figure 1 was obtained in the same way as in Example 1, except that instead of the polypropylene resin J, which contains a carboxyl group and has an MFR of 12 g / 10 min measured at 130°C, a polypropylene resin Y was used, which has a carboxyl group and an MFR of 45 g / 10 min measured at 130°C.

[0103] The melting points described in the descriptions of the respective example and comparison example are / were melting points measured at a temperature increase rate of 20°C / min using an automatic differential scan calorimeter (product number: DSC-60A) from Shimadzu Corporation.

[0104] Each molded packaging material obtained in the manner described above was evaluated based on the following evaluation procedure. The results are shown in Tables 1 to 3. [Table 1] [Table 2] [Table 3] <Evaluierungsverfahren der Laminierfestigkeit>

[0105] A test piece was produced by cutting a molded packaging material into a width of 15 mm, and the lamination strength of the test piece (the lamination strength of the first adhesive layer) was determined. 5 and the polypropylene layer (inner layer) 3 ) was measured using a tensile testing machine in the atmosphere at 80°C. (Evaluation standard) “⌾”... Laminating strength was 5 N / 15 mm width or more “O” ...Laminating strength was 3 N / 15 mm width or more, but less than 5 N / 15 mm “X” ...lamination strength was less than 3 N / 15 mm width <Evaluierungsverfahren der Elektrolyt-Beständigkeit>

[0106] A molded packaging material was cut to a width of 15 mm to produce measuring parts, and a solution in which lithium hexafluorophosphate salt was dissolved in a mixed solvent in which ethylene carbonate and diethylene carbonate were mixed together in a 1:1 volume ratio, so that the density was 1 mol / L, and the measuring part was placed in a wide-mouth bottle made of tetrafluoroethylene resin and stored in an oven at 85°C for one week, and then the measuring part was removed and the interface of the first adhesive layer was checked. 5 and the polypropylene layer (inner layer) 3 separated to measure the lamination strength (adhesive strength) between them. (Evaluation standard) “⌾” ...the measured adhesion strength has a retention rate of 90% or more with respect to the original adhesion strength “O” ...the measured adhesion strength has a retention rate of 60% or more, but less than 95%, based on the original adhesion strength “Δ” ...the measured adhesion strength has a retention rate of 30% or more, but less than 60%, relative to the original adhesion strength “X” ...the measured adhesion strength has a retention rate of less than 30% relative to the original adhesion strength (including those which were delaminated during immersion) <Evaluierungsverfahren der Dichtfunktion>

[0107] A seal release test was performed under conditions of 25°C and 80°C using a TENSILON RTA-100, manufactured by Orientale Co. Ltd., and a constant temperature tank TCF-III1-B, manufactured by Baldwin Co., Ltd., to evaluate the sealing function. The sealing conditions were tested for each molded packaging material at a sealing width of 5 mm, a sealing pressure of 0.3 MPa, a sealing time of 1 second, and sealing temperatures of 160°C and 180°C by heating both surfaces. (Sealing Function Evaluation Standard) “⌾” ...a strength of 30 N / 15 mm or more was obtained in both cases: sealed at 160°C and a seal release test was performed at 25°C; and sealed at 180°C, with a seal release test performed at 80°C “O” ...a strength of 25 N / 15 mm or more, but less than 30 N / 15 mm, was obtained in both cases: sealed at 160°C, with a seal-separation test performed at 25°C; and sealed at 180°C, with a seal-separation test performed at 80°C. “X” ...not as above (poor sealing function) <Evaluierungsverfahren der Lagerstabilität des Haftmittels (Prozessierlösung)>

[0108] The storage stability of the first adhesive (processing solution) used in each of the examples and comparison examples was evaluated as follows. Approximately 100 mL of each of the first adhesives (processing solutions) was placed in a glass container with an internal capacity of 110 mL and left to stand for one month at a temperature of 25°C. The condition of the adhesive solution after standing for one month was visually observed and evaluated based on the following evaluation standards. (Evaluation standard) “⌾” ...there was no cloudiness or thickening, and the external appearance and state of the solution did not change from the original state (no change: remained) “O” ...there was a slight cloudiness or thickening, but the fluidity was maintained (can be used as an adhesive without problems: passed) “X” ...there was a clouding and solidification

[0109] As can be seen from Tables 1 and 2, the molded packaging material of Examples 1 to 10 of the present invention had sufficient interlaminar strength and excellent electrolyte resistance and sealing properties. Furthermore, the first adhesives used in Examples 1 to 10 exhibited excellent storage stability.

[0110] On the other hand, the molded packaging material of comparison example 1, which uses a urethane-based adhesive as a first adhesive, exhibited poor electrolyte resistance. Furthermore, the molded packaging material of comparison example 2, which uses a polyolefin resin lacking a carboxyl group as a first adhesive, showed poor interlaminar strength, electrolyte resistance, and sealing performance. Additionally, the molded packaging material of comparison examples 3 and 4, which used a polyolefin resin containing a carboxyl group as a first adhesive and whose MFR measured at 130°C deviated from the range of 5 g / 10 min to 42 g / 10 min, also exhibited poor interlaminar strength and sealing performance.

[0111] The present invention claims priority from Japanese patent application number 2012-19811, filed on February 1, 2012, the entire contents of which are incorporated herein by reference. INDUSTRIAL APPLICABILITY

[0112] The molded packaging material according to the present invention can preferably be used as a housing for a secondary battery for use in, for example, laptops, mobile phones, automobiles or for a stationary-type lithium-ion secondary battery, and can also preferably be used as a packaging material for, for example, food products and pharmaceutical products, but it is not specifically limited to these uses. Reference symbol list 1. Molded packaging material 2. Heat-resistant resin layer (outer layer) 3 Polypropylene layer (inner layer) 4 layers of metal foil 4a Chemical conversion treatment surface of the inner side of the metal foil layer 5 Adhesive layer (first adhesive layer) 5a Inner surface of the adhesive layer 11 second adhesive (layer)< / ausgangsstoffe>

Claims

[1] A molded packaging material ( 1 ), showing: a heat-resistant resin layer ( 2 ) as an outer layer; a polypropylene layer ( 3 ) as an inner layer; and a metal foil layer ( 4 ), which is arranged between the heat-resistant resin layer and the polypropylene layer, where at least one inner surface ( 4a ) the metal foil layer is subjected to a chemical conversion treatment, and wherein the polypropylene layer is bonded to the chemically converted surface of an inner side of the metal foil layer by means of an adhesive layer ( 5 ) is laminated, and wherein the adhesive layer is formed by applying an adhesive to the chemically transformed surface of the inside of the metal foil layer, wherein the adhesive comprises at least an organic solvent, a polyolefin resin with a carboxyl group dissolved in the organic solvent and having an MFR of 5 g / 10 min to 42 g / 10 min, measured at 130°C, and a multifunctional isocyanate compound. [2] The molded packaging material as specified in claim 1, wherein the adhesive further comprises a polyolefin resin having a carboxyl group and a melting point of 120°C to 170°C in a manner dispersed in the organic solvent. [3] The molded packaging material as specified in claim 1 or 2, wherein the adhesive layer is formed by applying the adhesive to the chemically transformed surface of the inside of the metal foil layer and subsequently subjecting the applied adhesive to a firing treatment. [4] The molded packaging material as specified in claim 3, wherein the polypropylene layer is formed by an extrusion lamination process by laminating a polypropylene onto an inner surface of the adhesive layer which is formed by the flame treatment. [5] The molded packaging material as specified in any one of claims 1 to 4, wherein the polypropylene layer is formed as the inner layer from a copolymer resin which contains at least propylene and ethylene as a copolymerization component, has a melting point of 135°C to 155°C and has an MFR of 6 g / 10 min to 25 g / 10 min, measured at 230°C. [6] The molded packaging material as specified in any one of claims 1 to 5, wherein the molded packaging material is used as a battery casing. [7] The shaped packaging material as specified in any one of claims 1 to 5, wherein the shaped packaging material is used as a packaging material for food or pharmaceutical products. [8] A method for producing a shaped packaging material, comprising: a step of bonding a heat-resistant resin film to a surface of a metal foil using a second adhesive; a step of forming a first adhesive layer by applying a first adhesive to the other surface of the metal foil, wherein the first adhesive contains at least an organic solvent, a polyolefin resin with a carboxyl group dissolved in the organic solvent and having an MFR of 5 g / 10 min to 42 g / 10 min, measured at 130°C, and a multifunctional isocyanate compound; and a step of laminating a polypropylene layer as an inner layer onto a non-laminated surface of the first adhesive layer, wherein the metal foil is a metal foil in which an area of ​​the metal foil, onto which at least the first adhesive is to be applied, is subjected to a chemical transformation treatment. [9] The method for producing a molded packaging material as specified in claim 8, wherein the first adhesive further comprises a polyolefin resin having a carboxyl group and a melting point of 120°C to 170°C, in a manner dispersed in the organic solvent. [10] The method for producing a molded packaging material as specified in claim 8 or 9, wherein, after the application of the first adhesive, the first adhesive is heated to carry out a firing in order to form the first adhesive layer. [11] The method for producing a molded packaging material as specified in any one of claims 8 to 10, wherein a copolymer resin is used as the polypropylene of the inner layer, which contains at least propylene and ethylene as a copolymerization component, has a melting point of 135°C to 155°C and has an MFR of 6 g / 10 min to 25 g / 10 min, measured at 230°C.