JP5525938B2 - Molding packaging material and manufacturing method thereof - Google Patents

Description

  The present invention is suitable, for example, as a packaging material suitably used as a case for a secondary battery such as a notebook computer, a cellular phone, an in-vehicle use, a stationary lithium ion secondary battery, or a packaging material for foods and pharmaceuticals. It relates to packaging materials.

  In order to prevent chemical changes, deterioration, decay, etc. of the contents of food, pharmaceuticals, etc. in the packaging material, laminate packaging materials using metal foils with excellent oxygen and moisture barrier properties have been widely used. ing.

  On the other hand, in recent years, with the reduction in size and weight of various electronic devices such as OA devices such as personal computers, mobile phones, game machines, headphone stereos, electronic notebooks, etc., the viewpoint of reducing the size and weight of the battery of the power supply unit Therefore, lithium ion polymer secondary batteries are often used. In this lithium ion polymer secondary battery, when the electrolytic solution in the battery reacts with water to generate hydrofluoric acid, the performance of the battery deteriorates, or liquid leakage occurs due to corrosion of the aluminum foil. As a material used for a case (accommodating case) of a lithium ion polymer secondary battery, a laminate packaging material having a high sealing property using a metal foil having an excellent water vapor barrier property has been used.

  Case materials (packaging materials) for lithium ion polymer secondary batteries include an outer layer made of a heat-resistant resin film, an intermediate layer made of aluminum foil as a water vapor barrier layer, and a polyolefin film for sealing the polymer electrolyte of the contents A laminated packaging material in which inner layers are sequentially laminated and integrated is used.

  In order to increase the capacity as much as possible to fill the polymer electrolyte, the laminate packaging material is molded into a three-dimensional rectangular parallelepiped shape by overhang molding or deep drawing to produce a battery case.

  Forming an embossed type exterior body composed of at least a base material layer, an adhesive layer, a chemical conversion treatment layer, aluminum, a chemical conversion treatment layer, an acid-modified PP film layer, an extruded resin layer, and an innermost layer as a method for producing the laminate packaging material The laminated body is subjected to a chemical conversion treatment on both surfaces of aluminum, and a base material layer is adhered to one surface by a dry lamination method, and then acid-modified PP is applied and baked on the other chemical conversion treatment surface, and then the acid A method in which a modified PP surface and an innermost layer (cast PP) are laminated by an extrusion resin by a sandwich lamination method (see Patent Document 1), at least a base material layer, an adhesive layer, a chemical conversion treatment layer, aluminum, a chemical conversion treatment layer, an acid-modified PP It is a laminate that forms an embossed type exterior body composed of a coating layer, an extruded resin layer, and an innermost layer. After the base material layer is bonded to the treated surface by the dry laminating method, the untreated surface of the aluminum is subjected to chemical conversion treatment, the acid-modified PP is applied and baked on the chemical-treated surface, and then the acid-modified PP surface and the innermost layer are coated. A method of laminating (cast PP) with an extruded resin by a sandwich lamination method (see Patent Document 1) is known.

  Further, it is a laminate for forming an embossed type exterior body composed of at least a base material layer, an adhesive layer, a chemical conversion treatment layer, aluminum, a chemical conversion treatment layer, an acid-modified PP coating layer, and an innermost layer, After the chemical conversion treatment is performed and one chemical conversion treatment surface and the base material are laminated by the dry lamination method, the acid-modified PP is applied and baked on the other surface, and then the innermost layer is applied to the acid-modified PP surface by the thermal lamination method. Laminate that forms an embossed type exterior body composed of at least a base material layer, an adhesive layer, a chemical conversion treatment layer, aluminum, a chemical conversion treatment layer, an acid-modified PP film layer, and an innermost layer (see Patent Document 2) Then, after chemical conversion treatment is performed on one surface of aluminum, the chemical conversion treatment and the base material are laminated by a dry lamination method, then chemical conversion treatment is performed on another surface, and the acid-modified PP is applied and baked. Was followed, method (see Patent Document 2) the cast polypropylene oxide modified PP surface is laminated by a thermal lamination method is also known.

JP 2001-1727779 A JP 2001-176457 A

  However, when the acid-modified PP surface and the innermost layer (cast polypropylene film) are sandwich-laminated with an extruded resin as in the former prior art, sufficient laminate strength is obtained between the extruded resin layer and the innermost layer. There was a problem that it was difficult to be. In order to obtain a high laminate strength by this manufacturing method, it is necessary to provide a heating step as a subsequent step, but if such a heating step is provided, productivity is lowered. In addition, when the acid-modified PP surface and the innermost layer (cast polypropylene film) are sandwich-laminated with an extruded resin, they are bonded via the extruded resin, which increases the thickness of the resin layer on the inner surface side and reduces the weight. In addition, there is a risk that sufficient moisture barrier properties cannot be obtained. Furthermore, the unevenness of the embossed surface of the cast polypropylene film surface is easily damaged (easy to be crushed) by the heat of the extruded molten resin and the pressure from the pinching roll, and it is not possible to secure an appropriate sliding property. There was a problem that it was difficult to obtain sex.

  When the cast polypropylene film is laminated on the acid-modified PP surface by the thermal laminating method as in the latter prior art, the unevenness of the embossed surface of the cast polypropylene film is damaged by the heat of the hot roll for laminating. There is a problem that it is easy to receive (easy to be crushed), an appropriate slip property cannot be secured, and it is difficult to obtain excellent moldability.

  The present invention has been made in view of such a technical background, and is capable of sufficiently securing the laminate strength between the layers, and can provide an appropriate slip property during molding, thereby improving the moldability. It is an object of the present invention to provide a manufacturing method capable of manufacturing a packaging material for molding with sufficient productivity while ensuring sufficient laminate strength between layers.

  In order to achieve the above object, the present invention provides the following means.

[1] A molding packaging material comprising a heat-resistant resin layer as an outer layer, a polypropylene layer as an inner layer, and a metal foil layer disposed between both layers,
Chemical conversion treatment is performed on at least the inner surface of the metal foil layer, and the polypropylene layer is laminated on the inner surface of the metal foil layer via an acid-modified polypropylene layer,
The acid-modified polypropylene layer is formed by applying a treatment liquid containing acid-modified polypropylene to the inner surface of the metal foil layer, followed by baking treatment, and the inner side of the formed acid-modified polypropylene layer. Polypropylene is laminated on the surface by an extrusion laminating method to form the polypropylene layer,
The molding packaging material characterized in that the inner surface of the polypropylene layer is formed as an uneven surface having a ten-point average roughness Rz of 0.5 to 5.0 μm.

  [2] The uneven surface on the inner side of the polypropylene layer is such that the inner surface of the polypropylene layer has a ten-point average roughness Rz of 2 to 8 μm on the outer peripheral surface during the extrusion lamination. 2. The molding packaging material according to item 1, wherein the molding packaging material is formed by being pressed against the packaging material.

  [3] The molding packaging material according to item 1 or 2, wherein the acid-modified polypropylene has a melting point of 135 to 155 ° C.

  [4] The polypropylene layer as the inner layer is composed of a copolymer resin containing at least propylene and ethylene as copolymerization components, a melting point of 135 to 155 ° C., and an MFR of 6 to 25 g / 10 min. 4. The molding packaging material according to any one of items 1 to 3.

  [5] The molding packaging material according to any one of items 1 to 4, which is used as a battery case.

  [6] The molding packaging material according to any one of items 1 to 4, which is used as a packaging material for food or medicine.

[7] A step of bonding a heat-resistant resin film to one surface of the metal foil with an adhesive;
After applying a treatment liquid containing acid-modified polypropylene and a solvent to the other surface of the metal foil, baking is performed by heating to form an acid-modified polypropylene layer;
Laminating a polypropylene layer on the non-laminated surface of the acid-modified polypropylene layer by an extrusion laminating method,
As the metal foil, using a metal foil that has been subjected to chemical conversion treatment on at least the surface on which the treatment liquid is applied,
During lamination by the extrusion laminating method, the surface on the non-lamination side of the polypropylene layer is brought into pressure contact with the outer circumferential surface of a cooling roll having a 10-point average roughness Rz of 2 to 8 μm on the outer circumferential surface. A method of manufacturing a packaging material for molding.

  [8] The method for producing a molding packaging material according to item 7, wherein the acid-modified polypropylene has a melting point of 135 to 155 ° C.

  [9] The molding according to item 7 or 8 above, wherein a copolymer resin containing at least propylene and ethylene as copolymerization components, having a melting point of 135 to 155 ° C. and an MFR of 6 to 25 g / 10 min is used as the polypropylene. For manufacturing packaging materials.

  In the invention of [1], an acid-modified polypropylene layer is formed by applying a treatment liquid containing acid-modified polypropylene to the chemical conversion treatment surface on the inner side of the metal foil layer, followed by baking treatment. Since the polypropylene layer is formed by laminating polypropylene on the inner surface of the polypropylene layer by the extrusion laminating method, the laminate strength between the layers can be sufficiently secured. Therefore, for example, when used as a battery case, it is possible to prevent the laminate strength from being lowered due to the influence of the electrolyte, and the laminate strength is affected by the heat generated by repeated charge / discharge and the expansion and contraction of the packaging material. Decreasing can also be prevented, and sufficient sealing performance can be secured. In addition, since the inner surface of the polypropylene layer is formed as an uneven surface with Rz of 0.5 to 5.0 μm, it is appropriate when the molding packaging material of the present invention is molded into a molded body such as a battery case. Slidability can be secured (that is, adhesion can be prevented), and good moldability can be secured. In addition, since the polypropylene layer is formed by directly laminating the polypropylene on the inner surface of the acid-modified polypropylene layer by the extrusion laminating method (without the adhesive resin layer), the thickness of the resin layer on the inner surface side is reduced. It can be suppressed, the weight can be reduced, and the moisture barrier property can be sufficiently obtained. Moreover, since the chemical conversion treatment is performed on at least one surface of the metal foil layer, corrosion of the metal foil surface by the contents (battery electrolyte, food, medicine, etc.) can be sufficiently prevented.

  In the invention of [2], the irregular surface on the inner side of the polypropylene layer is a surface of the cooling roll whose inner surface of the polypropylene layer has an outer peripheral surface having a ten-point average roughness Rz of 2 to 8 μm during the extrusion lamination. Since it is formed by being pressed against the outer peripheral surface, an uneven surface having a 10-point average roughness Rz of 0.5 to 5.0 μm can be reliably formed on the inner surface of the polypropylene layer.

  In the invention [3], since the melting point of the acid-modified polypropylene is 135 to 155 ° C., the laminate strength between the acid-modified polypropylene and the polypropylene layer (inner layer) can be further increased.

  In the invention of [4], the polypropylene layer (inner layer) is formed of a copolymer resin having a melting point of 135 to 155 ° C. and an MFR of 6 to 25 g / 10 min. Therefore, sufficient heat resistance can be secured, and appropriate fluidity can be realized at the time of sealing, and excellent sealing performance can be secured.

  According to the invention of [5], a battery case material having a high interlayer laminate strength and excellent moldability is provided.

  According to the invention of [6], a food packaging material having a large interlayer laminate strength and excellent moldability or a pharmaceutical packaging material having a large interlayer laminate strength and excellent moldability is provided.

  In the invention of [7], after applying a heat-resistant resin film to one surface of the metal foil with an adhesive, and applying a treatment liquid containing acid-modified polypropylene and a solvent to the other surface of the metal foil. A step of forming an acid-modified polypropylene layer by baking by heating, and a step of laminating a polypropylene layer on an unlaminated surface of the acid-modified polypropylene layer by an extrusion laminating method. Since a metal foil having a chemical conversion treatment applied to the surface on which the treatment liquid is applied is used, a molding packaging material that can sufficiently secure the laminate strength between layers can be manufactured. Therefore, when the obtained packaging material is molded into, for example, a battery case, it is possible to prevent the laminate strength from being lowered due to the influence of the electrolyte, and to generate heat or expand / contract the packaging material due to repeated charge / discharge. It is possible to prevent the laminate strength from being lowered due to the influence of the above, and to ensure a sufficient sealing performance.

  Further, during lamination by the extrusion laminating method, the surface on the non-lamination side of the polypropylene layer is brought into pressure contact with the outer circumferential surface of the cooling roll having a 10-point average roughness Rz of 2 to 8 μm on the outer circumferential surface. An uneven surface with a 10-point average roughness Rz of 0.5 to 5.0 μm can be formed on the non-stacked side surface (inner surface), whereby the obtained packaging material can be used, for example, as a battery case or the like. Therefore, it is possible to ensure appropriate slipperiness (that is, to prevent adhesion) when molding into a molded product of the above, and to ensure good moldability.

  In addition, since the polypropylene is laminated directly on the non-laminated surface (inner surface) of the acid-modified polypropylene layer by an extrusion laminating method (without an adhesive resin layer), the thickness of the resin layer on the inner surface side is reduced. Thus, it is possible to reduce the weight of the packaging material for molding and to sufficiently secure the moisture barrier property. In addition, since at least the surface of the metal foil layer to which the treatment liquid is applied is subjected to chemical conversion treatment, the molding can sufficiently prevent corrosion of the metal foil surface by the contents (battery electrolyte, food, medicine, etc.) Packaging materials can be manufactured.

  In the invention of [8], since an acid-modified polypropylene having a melting point of 135 to 155 ° C. is used, a molding packaging material having a further increased laminate strength between the acid-modified polypropylene and the polypropylene layer (inner layer) is provided. Can be manufactured.

  In the invention of [9], as polypropylene (inner layer), a copolymer resin containing at least propylene and ethylene as a copolymerization component having a melting point of 135 to 155 ° C. and MFR of 6 to 25 g / 10 min is used. In addition to providing sufficient heat resistance, it is possible to produce a packaging material for molding that can achieve appropriate fluidity during sealing and ensure excellent sealing performance.

It is sectional drawing which shows one Embodiment of the packaging material for shaping | molding which concerns on this invention. It is a side view which shows an example of the manufacturing method of the packaging material for shaping | molding which concerns on this invention. It is sectional drawing which shows the conventional packaging material for shaping | molding. It is a side view which shows the conventional manufacturing method using the sandwich lamination method.

  One embodiment of the packaging material 1 for molding according to the present invention is shown in FIG. The molding packaging material 1 is formed into, for example, a substantially rectangular parallelepiped shape with an upper surface opened and used as a case of a lithium ion polymer secondary battery.

  In the molding packaging material 1, the heat-resistant resin layer (outer layer) 2 is laminated and integrated on one surface of the metal foil layer 4 via the adhesive layer 11, and the other surface of the metal foil layer 4. The polypropylene layer (inner layer) 3 is laminated and integrated with the acid-modified polypropylene layer 5 interposed therebetween.

  At least the inner surface (surface on the polypropylene layer 3 side) 4 a of the metal foil layer 4 is subjected to chemical conversion treatment, and the acid-modified polypropylene layer 5 is laminated on the inner chemical conversion treatment surface 4 a of the metal foil layer 4.

  The acid-modified polypropylene layer 5 is formed by applying a treatment liquid containing acid-modified polypropylene to the chemical conversion treatment surface 4 a inside the metal foil layer 4 and then performing a baking treatment by heating. Further, the polypropylene layer (inner layer) 3 is formed by laminating polypropylene on the inner surface 5a of the acid-modified polypropylene layer 5 formed by the baking by an extrusion laminating method.

  The inner surface 3a of the polypropylene layer 3 is formed as an uneven surface having a ten-point average roughness Rz of 0.5 to 5.0 μm. The ten-point average roughness Rz is a value measured according to JIS B0601-2001 (Appendix I).

  Since the packaging material for molding 1 having the above configuration can sufficiently secure the laminate strength between layers, when the packaging material 1 is molded into, for example, a battery case, the laminate strength decreases due to the influence of the electrolytic solution. It is possible to prevent the laminate strength from being lowered due to the effects of heat generation due to repeated charge and discharge and the expansion and contraction of the packaging material, thereby ensuring sufficient sealing performance. In addition, since the ten-point average roughness Rz of the inner surface 3a of the polypropylene layer 3 is 0.5 to 5.0 μm, it is possible to ensure an appropriate slipping property when molded into a molded body such as a battery case ( That is, it is possible to prevent close contact) and secure good moldability.

  Next, an example of a method for producing the molding packaging material 1 of the present invention will be described with reference to FIG. First, the stretched heat resistant resin film (heat resistant resin layer) 2 is bonded to one surface of the metal foil 4 with an adhesive 11 (adhesion process). For example, bonding is performed by a dry laminating method. As said metal foil 4, the metal foil by which the chemical conversion process was performed to the inner surface (surface on the side which apply | coats the process liquid used at the next process) 4a at least is used. You may use the metal foil 4 by which the chemical conversion process was performed on both surfaces.

  After the treatment liquid containing acid-modified polypropylene and a solvent is applied to the other surface (inner surface) 4a of the metal foil 4, baking is performed by heating to form an acid-modified polypropylene layer (film layer) 5. (Baking process). In this way, the laminated body 30 is obtained (refer FIG. 2).

  The concentration of the acid-modified polypropylene in the treatment liquid is preferably set to 10 to 30% by mass. Further, the solvent constituting the treatment liquid is not particularly limited, and examples thereof include toluene, methylcyclohexane, and acetic acid ethyl ester. In the treatment liquid, the acid-modified polypropylene is preferably dispersed in a solvent.

  The method for applying the treatment liquid is not particularly limited, and examples thereof include a gravure roll method.

  The heating temperature during the baking process is preferably set to 150 to 250 ° C. Adhesion of the acid-modified polypropylene layer 5 to the metal foil 4 can be sufficiently ensured by being 150 ° C. or higher, and deterioration of the acid-modified polypropylene can be suppressed by being 250 ° C. or less.

  Next, the polypropylene layer 3 is laminated on the non-laminated surface 5a of the acid-modified polypropylene layer 5 of the laminate 30 by an extrusion laminating method (extrusion laminating step). At the time of this extrusion lamination, as shown in FIG. 2, the laminate 30 and the extruded polypropylene 3X are sandwiched between a rubber roll 21 and a cooling roll 22. At this time, as the cooling roll 22, the cooling roll 22 having a 10-point average roughness Rz of 2 to 8 μm on the outer peripheral surface is used, and the non-laminated side surface 3 a of the polypropylene layer is used as the outer peripheral surface of the cooling roll 22. By press-contacting (see FIG. 2), the molding packaging material 1 of the present invention as shown in FIG. 1 is obtained.

  The material of the surface of the cooling roll 22 is not particularly limited, and for example, a general material such as stainless steel can be used.

  The ten-point average roughness Rz of the outer peripheral surface of the cooling roll 22 is set to 2 to 8 μm. When Rz exceeds 8 μm, it is difficult to adjust the thickness of the extruded resin, and the extruded resin 3 may be difficult to peel off from the cooling roll 22. When Rz is less than 2 μm, it is not possible to secure an appropriate sliding property when molding a molding packaging material into a molded body such as a battery case, and good moldability cannot be obtained.

  Although it does not specifically limit as the said heat resistant resin layer (outer layer) 2, For example, a nylon film, a polyester film, etc. are mentioned, These stretched films are used preferably. Among these, as the heat resistant resin layer 2, a biaxially stretched nylon film, a biaxially stretched polybutylene terephthalate (PBT) film, a biaxially stretched polyethylene terephthalate (PET) film or a biaxially stretched polyethylene naphthalate (PEN) film is used. Is particularly preferred. The nylon film is not particularly limited, and examples thereof include 6 nylon film, 6,6 nylon film, MXD nylon film, and the like. In addition, the said heat resistant resin layer 2 may be formed by the single layer, or may be formed by the multilayer which consists of PET film / nylon film, for example.

  The thickness of the heat resistant resin layer 2 is preferably 12 to 50 μm. When a polyester film is used, the thickness is preferably 12 to 50 μm, and when a nylon film is used, the thickness is preferably 15 to 50 μm. By setting it above the preferred lower limit value, it is possible to ensure a sufficient strength as a packaging material, and by setting it below the preferred upper limit value, it is possible to reduce stress during stretch molding or draw molding, and to improve moldability.

  The metal foil layer 4 plays a role of imparting gas barrier properties to the molding packaging material 1 to prevent oxygen and moisture from entering. Although it does not specifically limit as said metal foil layer 4, For example, aluminum foil, copper foil, etc. are mentioned, Aluminum foil is generally used. The thickness of the metal foil layer 4 is preferably 20 to 100 μm. When it is 20 μm or more, generation of pinholes during rolling when producing a metal foil can be prevented, and when it is 100 μm or less, stress during stretch forming or draw forming can be reduced and formability can be improved.

The metal foil layer 4 is subjected to chemical conversion treatment on at least the inner surface 4a (the surface on the acid-modified polypropylene layer 5 side). By such chemical conversion treatment, corrosion of the surface of the metal foil due to the contents (battery electrolyte, food, medicine, etc.) can be sufficiently prevented. For example, the metal foil is subjected to chemical conversion treatment by the following treatment. That is, for example, on the surface of the metal foil that has been degreased,
1) Aqueous solution comprising a mixture of phosphoric acid, chromic acid and fluoride metal salt 2) Aqueous solution comprising a mixture of phosphoric acid, chromic acid, fluoride metal salt and non-metal salt 3) Acrylic resin and / or phenolic resin Then, a chemical conversion treatment is performed by applying an aqueous solution composed of a mixture of phosphoric acid, chromic acid, and a fluoride metal salt, followed by drying.

  The acid-modified polypropylene layer 5 is a film (coating film) formed by applying a treatment liquid containing acid-modified polypropylene to the chemical conversion treatment surface 4a on the inner side of the metal foil layer 4 and then performing a baking treatment by heating. It is.

  Examples of the acid-modified polypropylene include polypropylene modified with an unsaturated carboxylic acid and / or a derivative thereof.

The unsaturated carboxylic acid and the derivative of the unsaturated carboxylic acid are not particularly limited.
Dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid, mesaconic acid,
Dicarboxylic anhydrides such as maleic anhydride, fumaric anhydride, itaconic anhydride, mesaconic anhydride,
Carboxyl group-containing monomers such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid,
Etc. Among these, maleic anhydride, acrylic acid, and methacrylic acid are preferably used, and maleic anhydride is particularly preferable.

  The method for producing the acid-modified polypropylene is not particularly limited. For example, a solution method in which polypropylene is dissolved in an organic solvent and reacted with an acid (such as maleic anhydride) in the presence of a radical generator. Examples thereof include a melting method in which polypropylene is heated and melted and reacted with an acid (such as maleic anhydride) in the presence of a radical generator. The acid-modified polypropylene thus obtained is dispersed in an organic solvent such as toluene, and this is used as a treatment liquid for the baking treatment.

  The melting point of the acid-modified polypropylene is preferably 135 to 155 ° C. When the melting point is within such a range, the laminate strength between the acid-modified polypropylene layer 5 and the polypropylene layer (inner layer) 3 can be sufficiently improved. The melting point of 135 to 155 ° C. means an acid-modified polypropylene resin having a peak temperature (melting point) of 135 to 155 ° C. measured by DSC (differential scanning calorimeter) at a heating rate of 20 ° C./min.

The amount of acid-modified polypropylene layer (film) 5 formed by the baking treatment is preferably set to 0.5 to 2.0 g / m ² in terms of solid content. When it is 0.5 g / m ² or more, sufficient adhesive strength can be obtained, and when it is 2.0 g / m ² or less, the drying time can be shortened and the processing efficiency can be improved. It is possible to prevent the solvent from remaining in the water vapor and to improve the water vapor barrier property.

The resin (extruded resin) constituting the polypropylene layer (inner layer) (sealant layer) 3 is not particularly limited. For example, 1) Copolymer resin 2 containing propylene and ethylene as copolymer components. ) Copolymer resin containing propylene, ethylene and butene as copolymerization component 3) Block copolymer resin containing propylene and ethylene as copolymerization component.

  An olefin-based thermoplastic elastomer may be blended with the copolymer resins 1) to 3).

  As the resin (extruded resin) constituting the polypropylene layer (inner layer) 3, it is preferable to use a copolymer resin containing at least propylene and ethylene as copolymerization components and having a melting point of 135 to 155 ° C. The copolymer resin having a melting point of 135 to 155 ° C. means a resin having a peak temperature (melting point) of 135 to 155 ° C. measured by DSC (differential scanning calorimeter) at a temperature rising rate of 20 ° C./min. . When the melting point is 135 ° C. or higher, sufficient heat resistance can be secured, and when the melting point is 155 ° C. or lower, excellent sealing properties can be secured.

  As the resin (extruded resin) constituting the polypropylene layer (inner layer) 3, it is preferable to use a copolymer resin containing at least propylene and ethylene as copolymerization components and an MFR of 6 to 25 g / 10 min. The MFR (melt flow rate) is a value measured according to JIS K7210-1999 (Condition M). When the MFR is 6 g / 10 min or more, extrusion lamination can be easily performed, and when the MFR is 25 g / 10 min or less, the fluidity of the resin at the time of sealing becomes appropriate and the sealing performance is further improved. Can be secured.

  The thickness of the polypropylene layer 3 is preferably 10 to 100 μm. When it is 10 μm or more, sufficient seal strength can be obtained, and when it is 100 μm or less, it is sufficiently prevented that the water vapor barrier from the end face is damaged. The polypropylene layer 3 may be composed of a single layer, or may be composed of a plurality of layers by performing co-extrusion of polypropylene or extrusion lamination of polypropylene twice. In the latter case, for example, if a polypropylene layer with high fluidity is arranged outside the polypropylene layer with low fluidity (innermost layer side), it is sufficient that the seal thickness becomes extremely thin due to abnormal flow of the polypropylene layer during sealing. Can be prevented.

  Although it does not specifically limit as an adhesive agent which comprises the said adhesive bond layer 11, For example, the two component hardening type urethane type adhesive agent etc. which contain a polyol component and an isocyanate component are mentioned. This two-component curing type urethane-based adhesive is suitably used particularly when bonded by a dry laminating method. Although it does not specifically limit as said polyol component, For example, polyester polyol, polyether polyol, etc. are mentioned. The isocyanate component is not particularly limited, and examples thereof include diisocyanates such as TDI (tolylene diisocyanate), HDI (hexamethylene diisocyanate), and MDI (methylene bis (4,1-phenylene) diisocyanate). . The thickness of the adhesive layer 11 is preferably set to 2 to 5 μm, particularly preferably 3 to 4 μm.

  As long as the effect of the present invention is not impaired, an inorganic or organic antiblocking agent or an amide slip agent may be added to the constituent resin.

  By forming the molding packaging material 1 of the present invention into various shapes such as a rectangular parallelepiped shape having a deep molding height (overhang molding, deep drawing molding, etc.), battery cases, food packaging materials, pharmaceutical packaging materials, etc. Etc. can be obtained. Since the battery case, food packaging material, and pharmaceutical packaging material obtained by such molding are prevented from entering the contents between the metal foil layer 4 and the acid-modified polypropylene layer 5, for example, the battery When used as a case, the laminate strength can be prevented from lowering due to the influence of the electrolyte, and the laminate strength can be affected by the heat generated by repeated charge / discharge and the expansion and contraction of the packaging material. Can be prevented, and sufficient sealing performance can be maintained.

  Next, specific examples of the present invention will be described, but the present invention is not particularly limited to these examples.

<Example 1>
A chemical conversion treatment solution composed of polyacrylic acid, a trivalent chromium compound, water and alcohol is applied to both surfaces of an aluminum foil 4 having a thickness of 40 μm, and dried at 180 ° C., so that the chromium adhesion amount becomes 10 mg / m ^2. After that, a 25 μm thick biaxially stretched polyamide film (biaxially stretched nylon film) (heat-resistant resin layer) 2 is dried on one surface of the aluminum foil 4 with a two-component curable urethane adhesive 11. After laminating and applying a treatment liquid (acid-modified polypropylene content: 25 mass%) in which acid-modified polypropylene having a melting point of 150 ° C. is dispersed in toluene on the other surface 4a of the aluminum foil 4 by a gravure roll method. by passing hot air drying oven at 200 ° C., subjected to baking by heating, Shi not form an acid-modified polypropylene layer 5 of fixed amount 2 g / m ² Then, as shown in FIG. 2, a propylene-ethylene copolymer resin extruded from the extrusion die 20 of the extruder (melting point measured by DSC is 140 ° C., MFR is 21 g / 10 minutes). The molding packaging material 1 shown in FIG. 1 is obtained by stacking and integrating 3X on the non-laminated surface (surface on which nothing is laminated) 5a of the acid-modified polypropylene layer 5 with a thickness of 20 μm by extrusion lamination. It was.

  During the extrusion laminating, as shown in FIG. 2, the laminate 30 and the extruded propylene-ethylene copolymer resin 3X are composed of a rubber roll 21 and a cooling roll 22 having a 10-point average roughness Rz of the outer peripheral surface of 5 μm. 1 to obtain a molding packaging material 1 shown in FIG.

< Reference Example 1 >
Instead of the treatment liquid in which acid-modified polypropylene having a melting point of 150 ° C. was dispersed in toluene, the treatment liquid was obtained by dispersing acid-modified polypropylene having a melting point of 160 ° C. in toluene (content ratio of acid-modified polypropylene: 25 1 was obtained in the same manner as in Example 1 except that (mass%) was used.

< Reference Example 2 >
As the extruded resin, instead of propylene-ethylene copolymer resin (melting point measured by DSC of 140 ° C., MFR of 21 g / 10 min), propylene-ethylene copolymer resin (melting point measured by DSC of 160 ° C., A molding packaging material 1 shown in FIG. 1 was obtained in the same manner as in Example 1 except that MFR was 21 g / 10 min.

< Reference Example 3 >
As the extruded resin, instead of propylene-ethylene copolymer resin (melting point measured by DSC of 140 ° C., MFR of 21 g / 10 min), propylene-ethylene copolymer resin (melting point measured by DSC of 140 ° C., A molding packaging material 1 shown in FIG. 1 was obtained in the same manner as in Example 1 except that MFR was 35 g / 10 min.

<Example 2 >
As the cooling roll, instead of a cooling roll having a 10-point average roughness Rz of 5 μm on the outer peripheral surface, a cooling roll having a 10-point average roughness Rz of 3 μm on the outer peripheral surface was used. Thus, the molding packaging material 1 shown in FIG. 1 was obtained.

<Example 3 >
Extrusion lamination of 20 μm-thick propylene-ethylene copolymer resin (melting point measured by DSC: 140 ° C., MFR: 21 g / 10 min) was carried out twice to form a copolymer resin layer 3 having a thickness of 40 μm. A molding packaging material 1 shown in FIG. 1 was obtained in the same manner as in Example 1 except that it was formed.

<Example 4 >
Instead of the biaxially stretched polyamide film having a thickness of 25 μm, a laminated film having a thickness of 27 μm (a bilayer laminated film of a biaxially stretched polyamide film having a thickness of 15 μm and a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm, a polyethylene terephthalate film, The molding packaging material 1 shown in FIG. 1 was obtained in the same manner as in Example 1 except that 2 was used.

<Comparative Example 1>
As the cooling roll, a cooling roll having a 10-point average roughness Rz of 1 μm on the outer peripheral surface was used instead of a cooling roll having a 10-point average roughness Rz of 5 μm on the outer peripheral surface. Thus, a molding packaging material 1 was obtained.

<Comparative example 2>
As the cooling roll, a cooling roll having a 10-point average roughness Rz of 11 μm on the outer peripheral surface was used instead of a cooling roll having a 10-point average roughness Rz of 5 μm on the outer peripheral surface. As a result, the extruded resin 3 was not easily peeled off from the cooling roll 22 and therefore could not be continuously produced. Therefore, various evaluations were not performed on Comparative Example 2.

<Comparative Example 3>
Apply a chemical conversion treatment solution consisting of polyacrylic acid, trivalent chromium compound, water, and alcohol on both sides of an aluminum foil with a thickness of 40 μm, and dry at 180 ° C. so that the chromium adhesion amount is 10 mg / m ^2. After that, a 25 μm-thick biaxially stretched polyamide film (biaxially stretched nylon film) (heat-resistant resin layer) is dry-laminated with a two-component curable urethane adhesive on one surface of the aluminum foil, On the other surface of the aluminum foil, an unstretched propylene-ethylene copolymer film (melting point measured by DSC was 140 ° C.) was dry-laminated with a two-component curable urethane adhesive to obtain a packaging material for molding. .

<Comparative Example 4>
A chemical conversion treatment solution composed of polyacrylic acid, a trivalent chromium compound, water and alcohol is applied to both surfaces of an aluminum foil 4 having a thickness of 40 μm, and dried at 180 ° C., so that the chromium adhesion amount becomes 10 mg / m ^2. After that, a 25 μm thick biaxially stretched polyamide film (biaxially stretched nylon film) (heat-resistant resin layer) 2 is dried on one surface of the aluminum foil 4 with a two-component curable urethane adhesive 11. After laminating and applying a treatment liquid (acid-modified polypropylene content: 25 mass%) in which acid-modified polypropylene having a melting point of 150 ° C. is dispersed in toluene on the other surface 4a of the aluminum foil 4 by a gravure roll method. by passing hot air drying oven at 200 ° C., subjected to baking by heating, Shi not form an acid-modified polypropylene layer 5 of fixed amount 2 g / m ² Then, as shown in FIG. 4, the extruded polypropylene extruded from the extrusion die 20 of the extruder onto the non-laminated surface (the surface on which nothing is laminated) 5a of the acid-modified polypropylene layer 5 is obtained. A molding packaging material 100 shown in FIG. 3 was obtained by laminating and integrating a propylene-ethylene random copolymer film (melting point measured by DSC: 140 ° C.) 31 through the resin 60 by sandwich lamination. The ten-point average roughness Rz of the outer peripheral surface of the cooling roll 22 is 5 μm.

<Comparative Example 5>
A chemical conversion treatment solution composed of polyacrylic acid, a trivalent chromium compound, water and alcohol is applied to both surfaces of an aluminum foil 4 having a thickness of 40 μm, and dried at 180 ° C., so that the chromium adhesion amount becomes 10 mg / m ^2. After that, a 25 μm thick biaxially stretched polyamide film (biaxially stretched nylon film) (heat-resistant resin layer) 2 is dried on one surface of the aluminum foil 4 with a two-component curable urethane adhesive 11. After laminating and applying a treatment liquid (acid-modified polypropylene content: 25 mass%) in which acid-modified polypropylene having a melting point of 150 ° C. is dispersed in toluene on the other surface 4a of the aluminum foil 4 by a gravure roll method. by passing hot air drying oven at 200 ° C., subjected to baking by heating, Shi not form an acid-modified polypropylene layer 5 of fixed amount 2 g / m ² Then, a laminate 30 is obtained, and then a propylene-ethylene random copolymer film (melting point measured by DSC is 140 ° C.) on the non-laminated surface (surface where nothing is laminated) 5a of the acid-modified polypropylene layer 5 is obtained. Was laminated and integrated by a heat laminating method to obtain a packaging material for molding.

  In addition, melting | fusing point described by description of each said Example and each comparative example is melting | fusing point measured by the temperature increase rate of 20 degree-C / min using the automatic differential scanning calorimeter (product number: DSC-60A) by Shimadzu Corporation. It is.

  Each molding packaging material obtained as described above was evaluated based on the following evaluation method. The results are shown in Table 1.

<Formability evaluation method>
Using an overhang molding machine (product number: TP-25C-X2) manufactured by Amada Co., Ltd., the packaging material for molding is stretched into a rectangular parallelepiped shape of 55 mm in length, 35 mm in width, and 8 mm in depth. Based on the following criteria The moldability was evaluated.
(Criteria)
“◎”… No pinholes and no cracks occurred “△”… Slightly some pinholes were generated but there were virtually no “×”… Pinholes and cracks were corners Occurred.

<Lamination strength evaluation method>
Cut the molding packaging material to a width of 15 mm to create a measurement piece, and pull the laminate strength of the measurement piece (laminate strength between the acid-modified polypropylene layer 5 and the polypropylene layer (inner layer) 3) under an atmosphere of 80 ° C. Measured with a testing machine.
(Criteria)
“◎”: A laminate strength of 5 N / 15 mm width or more “O”: A laminate strength of 3 N / 15 mm width or more and less than 5 N / 15 mm width “X”: Lamination strength is less than 3 N / 15 mm width.

<Electrolytic solution resistance evaluation method>
Cut the molding packaging material to a width of 15 mm to prepare a measurement piece, and a concentration of 1 mol / L of lithium hexafluorophosphate with respect to a mixed solvent in which ethylene carbonate and diethylene carbonate are mixed at a volume ratio of 1: 1. The solution dissolved in the above and the measurement piece are put into a wide-mouthed bottle made of tetrafluoroethylene resin and stored in an oven at 85 ° C. for one week, and then the measurement piece is taken out to remove the acid-modified polypropylene layer 5 and the polypropylene layer. (Inner layer) It peeled at the interface of 3, and the laminate strength (adhesion strength) between both was measured.
(Criteria)
“◎”: The measured adhesive strength is 90% or higher with respect to the initial adhesive strength. “◯”: The measured adhesive strength is 60% or higher with respect to the initial adhesive strength but less than 95%. ... Measured adhesive strength with respect to initial adhesive strength is 30% or more and less than 60% "x" ... Measured adhesive strength with respect to initial adhesive strength is less than 30% (delamination during immersion) Included).

<Seal performance evaluation method>
A seal peeling test was performed under conditions of 25 ° C. and 80 ° C. using Tensilon RTA-100 manufactured by Orientec Co., Ltd. and a constant temperature bath TCF-III1-B manufactured by Baldwin Co., Ltd., and the sealing performance was evaluated. The sealing conditions for each packaging material were 5 mm seal width, 0.3 MPa seal pressure, 1 second seal time, 160 ° C. and 180 ° C. double-sided heating.
(Seal performance criteria)
“◎”: A strength of 30 N / 15 mm or more was obtained in both cases of sealing at 160 ° C. and performing a seal peeling test at 25 ° C. and sealing at 180 ° C. and performing a seal peeling test at 80 ° C. “◯”: Strength at 25 N / 15 mm or more and less than 30 N / 15 mm in both cases of sealing at 160 ° C. and performing a seal peeling test at 25 ° C. and sealing at 180 ° C. and performing a seal peeling test at 80 ° C. Obtained “×”: those not corresponding to the above (poor sealing performance).

As is clear from Table 1, the packaging materials for molding of Examples 1 to 4 and Reference Examples 1 to 3 of the present invention have good sliding properties during molding, no pinholes and cracks are generated, and molding is performed. It was excellent in nature. In addition, the molding packaging materials of Examples 1 to 4 and Reference Examples 1 to 3 had sufficient laminate strength, and were excellent in electrolytic solution resistance and sealing performance.

  On the other hand, in the molding packaging material of Comparative Example 1, the slipping property at the time of molding was poor, and many pinholes were generated by overhang molding, and the moldability was poor. In Comparative Example 2, the extruded resin 3 was hardly peeled off from the cooling roll 22 and therefore could not be continuously produced. In the molding packaging material of Comparative Example 3, although the moldability was good, the laminate strength was insufficient and the electrolytic solution resistance was also inferior. Further, in the molding packaging material of Comparative Example 4, the unevenness on the inner surface of the propylene-ethylene random copolymer film layer 31 bonded by the sandwich laminate method disappears, and the slipperiness during molding is insufficient. Therefore, the moldability was inferior. Further, the molding packaging material of Comparative Example 5 was inferior in moldability.

  The molding packaging material according to the present invention is suitably used as a battery case for notebook computers, mobile phones, in-vehicle, stationary lithium ion polymer secondary batteries and the like. Although suitable as a packaging material for pharmaceuticals, it is not particularly limited to these uses.

1 ... Molding packaging material 2 ... Heat-resistant resin layer (outer layer)
3. Polypropylene layer (inner layer)
3a ... Inner surface of the polypropylene layer (surface on the non-laminated side)
4 ... Metal foil layer 4a ... Chemical conversion treatment surface 5 inside metal foil layer ... Acid-modified polypropylene layer 5a ... Inside surface of acid-modified polypropylene layer 11 ... Adhesive layer 22 ... Cooling roll

Claims (5)

A packaging material for molding comprising a heat-resistant resin layer as an outer layer, a polypropylene layer as an inner layer, and a metal foil layer disposed between these two layers,
Chemical conversion treatment is performed on at least the inner surface of the metal foil layer, and the polypropylene layer is laminated on the inner surface of the metal foil layer via an acid-modified polypropylene layer,
The acid-modified polypropylene layer was formed by applying a treatment liquid containing acid-modified polypropylene to the chemical conversion treatment surface inside the metal foil layer, and then baking at a heating temperature of 150 to 250 ° C. Polypropylene is laminated by extrusion lamination on the inner surface of the acid-modified polypropylene layer to form the polypropylene layer,
The polypropylene layer as the inner layer is composed of a copolymer resin containing at least propylene and ethylene as copolymerization components, having a melting point of 135 to 155 ° C., and an MFR of 6 to 25 g / 10 min.
The inner surface of the polypropylene layer is formed on an uneven surface having a ten-point average roughness Rz of 0.5 to 5.0 μm ,
It said processing liquid, wherein the solvent, mp dispersed in said solvent contains an acid-modified polypropylene one hundred and thirty-five to one hundred and fifty-five ° C., the concentration of 10 to 30% by mass Rukoto acid-modified polypropylene in the processing solution Molding packaging material.   The inner surface of the polypropylene layer is pressed against the outer peripheral surface of the cooling roll having a ten-point average roughness Rz of 2 to 8 μm on the outer peripheral surface during the extrusion lamination. The molding packaging material according to claim 1, wherein the packaging material is formed. The molding packaging material according to claim 1 or 2, which is used as a battery case. The molding packaging material according to claim 1 or 2, which is used as a packaging material for food or medicine. Adhering a heat-resistant resin film to one side of the metal foil with an adhesive;
On the other surface of the metal foil, solvent and a melting point which is dispersed in said solvent contains an acid-modified polypropylene 135-155 ° C., the treatment solution concentration Ru 10-30% by mass of the acid-modified polypropylene After coating, baking by heating at a heating temperature of 150 to 250 ° C. to form an acid-modified polypropylene layer;
A polypropylene layer made of a copolymer resin containing at least propylene and ethylene as copolymerization components, having a melting point of 135 to 155 ° C., and an MFR of 6 to 25 g / 10 min is extruded on the non-laminated surface of the acid-modified polypropylene layer. And laminating by a laminating method,
As the metal foil, using a metal foil that has been subjected to chemical conversion treatment on at least the surface on which the treatment liquid is applied,
During lamination by the extrusion laminating method, the surface on the non-lamination side of the polypropylene layer is brought into pressure contact with the outer circumferential surface of a cooling roll having a 10-point average roughness Rz of 2 to 8 μm on the outer circumferential surface. A method of manufacturing a packaging material for molding.

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