JP6596870B2 - Method for producing molded body for battery packaging material - Google Patents

Description

  The present invention relates to a method for producing a molded article for battery packaging material in which ink is suitably printed on the outer surface.

  Conventionally, various types of batteries have been developed. In any battery, a packaging material is an indispensable member for sealing battery elements such as electrodes and electrolytes. Conventionally, metal packaging materials have been widely used as battery packaging, but in recent years, with the increasing performance of electric vehicles, hybrid electric vehicles, personal computers, cameras, mobile phones, etc., batteries are required to have various shapes. At the same time, there is a demand for reduction in thickness and weight. However, metal battery packaging materials that have been widely used in the past have the disadvantages that it is difficult to follow the diversification of shapes and that there is a limit to weight reduction.

  Therefore, a film-like laminate in which a base material layer / adhesive layer / metal layer / sealant layer are sequentially laminated is proposed as a battery packaging material that can be easily processed into various shapes and can be made thinner and lighter. (For example, refer to Patent Document 1). Such a film-shaped battery packaging material is formed so that the battery element can be sealed by causing the sealant layers to face each other and heat-sealing the peripheral portion by heat sealing.

  In various packaging materials formed by the laminates as described above, ink is printed on the surface of the base material layer to form barcodes, patterns, characters, etc., and then bonded onto the base material layer on the printed side A method of printing on a packaging material (generally referred to as intermediate printing) by a method of laminating an agent and a metal foil is widely adopted. However, when such a printing surface exists between the base material layer and the metal layer, the adhesion between the base material layer and the metal layer is lowered, and delamination is likely to occur between the layers. In particular, since high safety is required for a battery to which the battery packaging material is applied, such a method of printing by intermediate printing is avoided in the battery packaging material. Therefore, conventionally, when printing a barcode or the like on a battery packaging material, a method of sticking a seal on which a print is formed on the surface of a base material layer is generally employed.

  However, when the seal on which the print is formed is affixed to the surface of the base material layer, the thickness and weight of the battery packaging material increase. Therefore, from the recent trend of further reduction in thickness and weight of battery packaging materials, a method of printing directly on the surface of the base material layer of the battery packaging material by ink printing has been studied.

  As a method for printing directly on the surface of the base material layer of the battery packaging material by ink printing, pad printing (also referred to as tampo printing) is known. Pad printing is a printing method as follows. First, ink is poured into a concave portion of a flat plate in which a pattern to be printed is etched. Next, the silicon pad is pressed from above the concave portion to transfer the ink to the silicon pad. Next, the ink transferred to the surface of the silicon pad is transferred to the object to be printed to form a print on the object to be printed. In such pad printing, the ink is transferred to the object to be printed using an elastic silicon pad or the like. Therefore, it is easy to print on the surface of the battery packaging material after molding, and the battery element is made of the battery packaging material. After sealing, the battery can be printed.

  By the way, in the battery packaging material, when enclosing the battery element, it is molded with a mold to form a space for accommodating the battery element. There is a problem that cracks and pinholes are likely to occur in the metal layer at the flange portion of the mold due to the battery packaging material being stretched during this molding. In order to solve such a problem, the surface of the base material layer of the battery packaging material is coated with a lubricant, or the lubricant bleed out on the surface of the sealant layer is transferred to the surface of the base material layer in a roll state. A method for improving the slipperiness of the base material layer is known. By adopting such a method, the battery packaging material is easily drawn into the mold during molding, and cracks and pinholes in the battery packaging material can be suppressed. In particular, from the recent demands for thinning and light weight of battery packaging materials, it is desirable to increase the slipperiness of the battery packaging material by making a lubricant present on the surface of the base material layer of the battery packaging material.

JP 2008-287971 A

  However, when the present inventors examined, when a lubricant was present on the surface of the base material layer to improve the moldability of the battery packaging material, the ink was repelled on the surface of the base material layer, and the ink was It has become clear that fixing may be difficult, and a missing portion where ink is not formed may occur. In particular, it has been clarified that printability tends to be insufficient when printing is performed by pad printing.

Furthermore, the battery packaging material is generally manufactured as a strip-shaped laminated film in a production line, and stored, transported, etc. as a wound body obtained by winding the film in a roll shape. And at the time of manufacture of a battery, the packaging material for batteries is unwound from a winding body, and it cuts and uses it so that it may become a predetermined shape according to the product specification of a battery. When the wound body of the battery packaging material is stored and transported for a long period of time, the lubricant bleed out from the sealant layer may adhere to the surface of the base material layer, and the printability may deteriorate.
Under such circumstances, the main object of the present invention is to provide a method for producing a molded article for battery packaging material in which ink is suitably printed on the outer surface.

  The present inventors have intensively studied to solve the above problems. As a result, at least a process of preparing a battery packaging material in which a base material layer, a metal layer, and a sealant layer are sequentially laminated, a molding process of cold-molding the battery packaging material, and the molding process Ink is applied to the outer surface by employing a method for producing a molded article for battery packaging material, which comprises a surface modification step for surface-modifying the outer surface of the base material layer of the battery packaging material before or after. Has been found that a molded product of battery packaging material can be suitably printed. The present invention has been completed by further studies based on these findings.

That is, this invention provides the invention of the aspect hung up below.
Item 1. At least a step of preparing a battery packaging material in which a base material layer, a metal layer, and a sealant layer are sequentially laminated;
A molding step of cold-molding the battery packaging material;
Before or after the molding step, a surface modification step for surface-modifying the outer surface of the base material layer of the battery packaging material;
The manufacturing method of the packaging material molded object for batteries provided with.
Item 2. Item 2. The method for producing a molded article for battery packaging material according to Item 1, wherein the surface modification treatment is corona treatment.
Item 3. Item 3. The method for producing a molded article for battery packaging material according to Item 1 or 2, wherein the surface modification step is performed after the molding step.
Item 4. Item 4. The method for producing a molded article for battery packaging material according to any one of Items 1 to 3, wherein the surface modification treatment is performed only on a part of the outer surface of the base material layer of the battery packaging material.
Item 5. Item 5. The method for producing a molded article for battery packaging material according to any one of Items 1 to 4, further comprising a printing step of printing ink on an outer surface of the base material layer after the surface modification step.
Item 6. Item 6. The method for producing a molded article for battery packaging material according to Item 5, wherein the printing step is performed by pad printing.
Item 7. Item 1 is prepared by preparing a winding body of a battery packaging material as the battery packaging material, and cutting the battery packaging material unwound from the winding body into a predetermined size. 6. A method for producing a battery packaging material according to any one of 6 above.
Item 8. Item 8. The method for producing a packaging material for a battery according to any one of Items 1 to 7, wherein a lubricant is present on the surface of the base material layer.
Item 9. Item 9. The method for producing a molded article for battery packaging material according to any one of Items 1 to 8, wherein the surface tension of the portion modified by the surface modification treatment is 35 mN / m or more.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the packaging material molded object for batteries by which the ink was suitably printed on the outer surface can be provided.

It is a schematic diagram which shows the formation process of the packaging material for batteries of this invention. It is a figure which shows an example of the cross-section of A part of the packaging material molded object for batteries obtained by the formation process of FIG. It is a figure which shows an example of the cross-section of A part of the packaging material molded object for batteries obtained by the formation process of FIG.

  The method for producing a molded article for battery packaging material according to the present invention comprises a step of preparing a battery packaging material in which at least a base material layer, a metal layer, and a sealant layer are sequentially laminated, and cooling the battery packaging material. It is characterized by comprising a molding step for performing an intermediate molding and a surface modification step for subjecting the outer surface of the base material layer of the battery packaging material to a surface modification treatment before or after the molding step. Hereafter, the manufacturing method of the packaging material molded object for batteries of this invention is explained in full detail.

  In the method for producing a molded article for battery packaging material of the present invention, first, a battery packaging material 10 in which at least a base material layer, a metal layer, and a sealant layer are sequentially laminated is prepared. In the molded article for battery packaging material of the present invention, the laminated structure of the battery packaging material 10 used in the molding process and the surface modification process and the composition of each layer are as described in detail later.

  Next, a battery packaging material forming step and a surface modification step are performed. Any of the molding process and the surface modification process of the battery packaging material may be performed first, but it is preferable to perform the surface modification process after the molding process. As will be described later, this makes it possible to avoid performing the molding process in a state where the surface state of the base material layer is changed due to the surface modification treatment and the moldability is lowered. Moreover, it can also be avoided that the surface state of the surface of the base material layer subjected to the surface modification treatment is changed by the subsequent molding process and the printability of the ink is lowered.

(Molding process)
For example, as shown in the schematic diagram of FIG. 1, in the molding step, the battery packaging material 10 is cold-molded to form a battery packaging material molded body 11. The conditions for cold forming are not particularly limited, and usually, a concave portion is formed from the sealant layer 4 side to the base material layer 1 side of the battery packaging material using a male mold and a female mold. In the battery of the present invention to be described later, the battery element is enclosed in the space formed by the recess.

  The pressing pressure (surface pressure) of the mold at the time of molding is not particularly limited, and can be, for example, 0.3 to 1.0 MPa. Moreover, it does not restrict | limit especially as cold forming temperature, For example, about 10-30 degreeC is mentioned. It does not restrict | limit especially as shaping | molding depth (depth of a recessed part), For example, about 1.0-10.0 mm is mentioned.

  As the battery packaging material, it is preferable to prepare a winding body of the battery packaging material, and cut the battery packaging material unwound from the winding body into a predetermined size to perform the forming step. As described above, when stored and transported for a long time in the state of a winding body for battery packaging material, the lubricant bleeded out from the sealant layer may adhere to the surface of the base material layer, which may reduce the printability. . On the other hand, when the battery packaging material unwound from such a wound body is used by adopting the method for producing a battery packaging material molded body of the present invention, the ink is applied to the outer surface. A suitably printed battery packaging material molded body can be produced.

(Surface modification process)
In the surface modification step, the outer surface (surface opposite to the metal layer 3) of the base material layer 1 of the battery packaging material is subjected to surface modification treatment. The surface modification step is performed before or after the molding step. As described above, in the present invention, the surface modification step is preferably performed after the molding step.

  The surface modification treatment is not particularly limited as long as the printability of ink on the outer surface of the base material layer 1 is improved. For example, corona treatment, plasma treatment, flame treatment, ionizing radiation irradiation treatment, blast treatment, oxidation treatment. , Ozone treatment, UV ozone treatment and the like. Among these, the corona treatment is particularly preferable because the printability of the ink on the outer surface of the base material layer 1 is particularly improved.

  The conditions for the surface modification treatment are not particularly limited. For example, the surface modification is performed so that the surface tension of the portion modified by the surface modification treatment is 35 mN / m or more, further 36 mN / m or more. It is preferable to carry out the treatment. In the present invention, the upper limit of the surface tension is, for example, about 40 mN / m. The surface tension is a value measured by a method based on JIS K6768: 1999, and the specific method is as described in the examples.

  In the surface modification step, the surface modification treatment is preferably performed only on a part of the outer surface of the base material layer 1 of the battery packaging material. For example, when the portion to be subjected to the surface modification treatment is substantially limited only to the area necessary for printing the ink, the portion to be printed with the ink is subjected to the surface modification treatment. Even when the printing property of the ink is excellent and the molding step is performed after the surface modification step, it is possible to suppress a decrease in moldability due to the surface modification step. Furthermore, it is preferable from the viewpoint of economy that the surface modification treatment is performed only on a part of the outer surface of the base material layer 1 of the battery packaging material.

(Printing process)
In the manufacturing method of the battery packaging material molded body of the present invention, a printing step of printing ink on the outer surface of the base material layer 1 may be further provided after the surface modification step. By providing the printing process, a battery packaging material molded body in which ink is suitably printed on the outer surface of the battery packaging material molded body is obtained. The printing process is particularly preferably performed after the molding process and the surface modification process.

  The printing method is not particularly limited, and includes pad printing, ink jet printing, thermal transfer printing, laser printing, ink transfer printing, hot stamp printing, and the like. Among these, pad printing is preferable when the printing process is performed after the molding process. In the method for producing a molded article for battery packaging material of the present invention, the outer surface of the base material layer 1 is subjected to surface modification treatment, so that the outer surface of the battery packaging material can be applied to the outer surface of the battery packaging material even by pad printing. Ink printing can be suitably performed. Accordingly, for example, a barcode, a pattern, a character, or the like can be suitably formed on at least a part of the surface of the battery packaging material molded body. The ink used for printing is not particularly limited, and a known ink can be used. For example, a photocurable ink that is cured by irradiation with ultraviolet rays or the like can be used.

Laminated structure of battery packaging material As shown in FIG. 2, the battery packaging material prepared in the method for producing a battery packaging material molded body of the present invention includes at least a base material layer 1, a metal layer 3, and a sealant layer. 4 consists of the laminated body laminated | stacked one by one. In the battery packaging material, the base material layer 1 is the outermost layer, and the sealant layer 4 is the innermost layer. That is, when the battery is assembled, the sealant layers 4 positioned at the periphery of the battery element are thermally welded to seal the battery element, thereby sealing the battery element.

  As shown in FIG. 2, the battery packaging material may be provided with an adhesive layer 2 between the base material layer 1 and the metal layer 3 as necessary for the purpose of improving the adhesion. In addition, as shown in FIG. 3, an adhesive layer 5 may be provided between the metal layer 3 and the sealant layer 4 as necessary for the purpose of improving the adhesion.

Composition of each layer forming base material for battery [base material layer 1]
In the battery packaging material, the base material layer 1 is a layer located in the outermost layer. The material for forming the base material layer 1 is not particularly limited as long as it has insulating properties. Examples of the material for forming the base material layer 1 include polyester, polyamide, epoxy resin, acrylic resin, fluorine resin, polyurethane, silicon resin, phenol resin, polyetherimide, polyimide, and a mixture or copolymer thereof. Can be mentioned.

  Specific examples of the polyester include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyethylene isophthalate, polycarbonate, copolymerized polyester mainly composed of ethylene terephthalate, butylene terephthalate as a repeating unit. Examples thereof include a copolymer polyester mainly used. The copolymer polyester mainly composed of ethylene terephthalate is a copolymer polyester that polymerizes with ethylene isophthalate mainly composed of ethylene terephthalate (hereinafter, polyethylene (terephthalate / isophthalate)). Abbreviated), polyethylene (terephthalate / isophthalate), polyethylene (terephthalate / adipate), polyethylene (terephthalate / sodium sulfoisophthalate), polyethylene (terephthalate / sodium isophthalate), polyethylene (terephthalate / phenyl-dicarboxylate) And polyethylene (terephthalate / decanedicarboxylate). In addition, as a copolymer polyester mainly composed of butylene terephthalate as a repeating unit, specifically, a copolymer polyester that polymerizes with butylene isophthalate having butylene terephthalate as a repeating unit (hereinafter referred to as polybutylene (terephthalate / isophthalate) For example), polybutylene (terephthalate / adipate), polybutylene (terephthalate / sebacate), polybutylene (terephthalate / decanedicarboxylate), polybutylene naphthalate and the like. These polyesters may be used individually by 1 type, and may be used in combination of 2 or more type. Polyester has the advantage of being excellent in electrolytic solution resistance and less likely to cause whitening due to the adhesion of the electrolytic solution, and is suitably used as a material for forming the base material layer 1.

  Specific examples of polyamides include aliphatic polyamides such as nylon 6, nylon 66, nylon 610, nylon 12, nylon 46, and copolymers of nylon 6 and nylon 6,6; terephthalic acid and / or Nylon 6I, Nylon 6T, Nylon 6IT, Nylon 6I6T (I represents isophthalic acid, T represents terephthalic acid) and the like, which contain a structural unit derived from isophthalic acid, Polyamides containing aromatics such as silylene adipamide (MXD6); Alicyclic polyamides such as polyaminomethylcyclohexyl adipamide (PACM6); and lactam components and isocyanate components such as 4,4′-diphenylmethane-diisocyanate Polymerized polyamide, co-weight Polyester amide copolymer and polyether ester amide copolymer is a copolymer of polyamide and polyester and polyalkylene ether glycol; copolymers thereof, and the like. These polyamides may be used individually by 1 type, and may be used in combination of 2 or more type. The stretched polyamide film is excellent in stretchability, can prevent whitening due to resin cracking of the base material layer 1 during molding, and is suitably used as a material for forming the base material layer 1.

  The base material layer 1 may be formed of a uniaxially or biaxially stretched resin film, or may be formed of an unstretched resin film. Among them, a uniaxially or biaxially stretched resin film, in particular, a biaxially stretched resin film has improved heat resistance by orientation crystallization, and thus is suitably used as the base material layer 1. Moreover, the base material layer 1 may be formed by coating the above-mentioned raw material on the metal layer 3.

  Among these, as a resin film which forms the base material layer 1, Preferably nylon and polyester, More preferably, biaxially stretched nylon, biaxially stretched polyester, Most preferably, biaxially stretched nylon is mentioned.

  The base material layer 1 can also be laminated with at least one of resin films and coatings of different materials in order to improve pinhole resistance and insulation when used as a battery package. Specific examples include a multilayer structure in which a polyester film and a nylon film are laminated, and a multilayer structure in which a biaxially stretched polyester and a biaxially stretched nylon are laminated. When making the base material layer 1 into a multilayer structure, each resin film may be adhere | attached through an adhesive agent, and may be laminated | stacked directly without an adhesive agent. In the case of bonding without using an adhesive, for example, a method of bonding in a hot melt state such as a co-extrusion method, a sand lamination method, or a thermal laminating method can be mentioned. Moreover, when making it adhere | attach through an adhesive agent, the adhesive agent to be used may be a two-component curable adhesive, or a one-component curable adhesive. Further, the bonding mechanism of the adhesive is not particularly limited, and may be any of a chemical reaction type, a solvent volatilization type, a heat melting type, a hot pressure type, an electron beam curing type such as UV and EB, and the like. As an adhesive component, polyester resin, polyether resin, polyurethane resin, epoxy resin, phenol resin resin, polyamide resin, polyolefin resin, polyvinyl acetate resin, cellulose resin, (meth) acrylic resin Resins, polyimide resins, amino resins, rubbers, and silicon resins can be used.

  In the present invention, a lubricant is preferably attached to the surface of the base material layer 1 from the viewpoint of improving the moldability of the battery packaging material. Although it does not restrict | limit especially as a lubricant, Preferably an amide type lubricant is mentioned. Specific examples of the amide-based lubricant include saturated fatty acid amide, unsaturated fatty acid amide, substituted amide, methylolamide, saturated fatty acid bisamide, unsaturated fatty acid bisamide, and the like. Specific examples of the saturated fatty acid amide include lauric acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, hydroxy stearic acid amide and the like. Specific examples of the unsaturated fatty acid amide include oleic acid amide and erucic acid amide. Specific examples of the substituted amide include N-oleyl palmitate, N-stearyl stearate, N-stearyl oleate, N-oleyl stearate, N-stearyl erucamide, and the like. Specific examples of methylolamide include methylol stearamide. Specific examples of saturated fatty acid bisamides include methylene bis stearamide, ethylene biscapric acid amide, ethylene bis lauric acid amide, ethylene bis stearic acid amide, ethylene bishydroxy stearic acid amide, ethylene bisbehenic acid amide, hexamethylene bis stearic acid amide. Examples include acid amide, hexamethylene bisbehenic acid amide, hexamethylene hydroxystearic acid amide, N, N′-distearyl adipic acid amide, N, N′-distearyl sebacic acid amide, and the like. Specific examples of unsaturated fatty acid bisamides include ethylene bisoleic acid amide, ethylene biserucic acid amide, hexamethylene bisoleic acid amide, N, N′-dioleyl adipic acid amide, N, N′-dioleyl sebacic acid amide Etc. Specific examples of the fatty acid ester amide include stearoamidoethyl stearate. Specific examples of the aromatic bisamide include m-xylylene bis stearic acid amide, m-xylylene bishydroxy stearic acid amide, N, N′-cysteallyl isophthalic acid amide and the like. One type of lubricant may be used alone, or two or more types may be used in combination.

  As thickness of the base material layer 1, about 10-50 micrometers, for example, Preferably about 12-30 micrometers is mentioned.

[Adhesive layer 2]
In the battery packaging material, the adhesive layer 2 is a layer provided as necessary in order to adhere the base material layer 1 and the metal layer 3.

  The adhesive layer 2 is formed of an adhesive capable of adhering the base material layer 1 and the metal layer 3. The adhesive used for forming the adhesive layer 2 may be a two-component curable adhesive or a one-component curable adhesive. Furthermore, the adhesive mechanism of the adhesive used for forming the adhesive layer 2 is not particularly limited, and may be any of a chemical reaction type, a solvent volatilization type, a heat melting type, a hot pressure type, and the like.

  Specific examples of the resin component of the adhesive that can be used to form the adhesive layer 2 include polyesters such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyethylene isophthalate, polycarbonate, and copolyester. Resin; Polyether adhesive; Polyurethane adhesive; Epoxy resin; Phenol resin resin; Polyamide resin such as nylon 6, nylon 66, nylon 12, copolymer polyamide; polyolefin, acid-modified polyolefin, metal-modified polyolefin, etc. Polyolefin resin; polyvinyl acetate resin; cellulose adhesive; (meth) acrylic resin; polyimide resin; urea resin, melamine resin and other amino resins; chloroprene rubber, nitrile rubber, styrene - rubbers such as butadiene rubber, silicone resin; fluorinated ethylene propylene copolymer, and the like. These adhesive components may be used individually by 1 type, and may be used in combination of 2 or more type. The combination mode of two or more kinds of adhesive components is not particularly limited. For example, as the adhesive component, a mixed resin of polyamide and acid-modified polyolefin, a mixed resin of polyamide and metal-modified polyolefin, polyamide and polyester, Examples thereof include a mixed resin of polyester and acid-modified polyolefin, and a mixed resin of polyester and metal-modified polyolefin. Among these, extensibility, durability under high-humidity conditions, anti-hypertensive action, thermal deterioration-preventing action during heat sealing, etc. are excellent, and a decrease in lamination strength between the base material layer 1 and the metal layer 3 is suppressed. From the viewpoint of effectively suppressing the occurrence of delamination, a polyurethane two-component curable adhesive; polyamide, polyester, or a blended resin of these with a modified polyolefin is preferable.

  The adhesive layer 2 may be multilayered with different adhesive components. When the adhesive layer 2 is multilayered with different adhesive components, from the viewpoint of improving the lamination strength between the base material layer 1 and the metal layer 3, the adhesive component disposed on the base material layer 1 side is used as the base material layer 1. It is preferable to select a resin having excellent adhesion to the metal layer 3 and to select an adhesive component having excellent adhesion to the metal layer 3 as the adhesive component disposed on the metal layer 3 side. When the adhesive layer 2 is multilayered with different adhesive components, specifically, the adhesive component disposed on the metal layer 3 side is preferably an acid-modified polyolefin, a metal-modified polyolefin, a polyester and an acid-modified polyolefin. And a resin containing a copolyester.

  About the thickness of the contact bonding layer 2, about 2-50 micrometers, for example, Preferably about 3-25 micrometers is mentioned.

[Metal layer 3]
In the battery packaging material, the metal layer 3 is a layer that functions as a barrier layer for preventing moisture, oxygen, light, and the like from entering the battery, in addition to improving the strength of the packaging material. Specific examples of the metal forming the metal layer 3 include metal foils such as aluminum, stainless steel, and titanium. Among these, aluminum is preferably used. In order to prevent wrinkles and pinholes during the production of the packaging material, soft aluminum, for example, annealed aluminum (JIS A8021P-O) or (JIS A8079P-O) is used as the metal layer 3 in the present invention. Is preferred.

  About the thickness of the metal layer 3, about 10-200 micrometers is preferable, for example, Preferably it is about 20-100 micrometers.

  Further, the metal layer 3 is preferably subjected to chemical conversion treatment on at least one surface, preferably at least the surface on the sealant layer 4 side, and more preferably both surfaces, for the purpose of stabilizing adhesion, preventing dissolution and corrosion, and the like. . Here, the chemical conversion treatment is a treatment for forming an acid-resistant film on the surface of the metal layer 3. The chemical conversion treatment is, for example, chromate chromate treatment using a chromic acid compound such as chromium nitrate, chromium fluoride, chromium sulfate, chromium acetate, chromium oxalate, chromium biphosphate, chromate acetylacetate, chromium chloride, potassium sulfate chromium, etc. ; Phosphoric acid chromate treatment using phosphoric acid compounds such as sodium phosphate, potassium phosphate, ammonium phosphate, polyphosphoric acid; aminated phenol heavy consisting of repeating units represented by the following general formulas (1) to (4) Examples thereof include chromate treatment using a coalescence. In the aminated phenol polymer, the repeating units represented by the following general formulas (1) to (4) may be included singly or in any combination of two or more. Also good.

In general formulas (1) to (4), X represents a hydrogen atom, a hydroxyl group, an alkyl group, a hydroxyalkyl group, an allyl group or a benzyl group. R ¹ and R ² are the same or different and represent a hydroxyl group, an alkyl group, or a hydroxyalkyl group. In the general formulas (1) to (4), examples of the alkyl group represented by X, R ¹ and R ² include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, C1-C4 linear or branched alkyl groups, such as a tert- butyl group, are mentioned. Examples of the hydroxyalkyl group represented by X, R ¹ and R ² include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, 3- A linear or branched chain having 1 to 4 carbon atoms substituted with one hydroxy group such as hydroxypropyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group An alkyl group is mentioned. In the general formulas (1) to (4), X is preferably any one of a hydrogen atom, a hydroxyl group, and a droxyalkyl group. The number average molecular weight of the aminated phenol polymer composed of the repeating units represented by the general formulas (1) to (4) is, for example, about 500 to about 1,000,000, preferably about 1000 to about 20,000.

  In addition, as a chemical conversion treatment method for imparting corrosion resistance to the metal layer 3, a metal oxide such as aluminum oxide, titanium oxide, cerium oxide, tin oxide, or barium sulfate fine particles dispersed in phosphoric acid is coated. A method of forming a corrosion-resistant treatment layer on the surface of the metal layer 3 by performing a baking treatment at 150 ° C. or higher can be mentioned. Moreover, you may form the resin layer which crosslinked the cationic polymer with the crosslinking agent on the corrosion-resistant process layer. Here, as the cationic polymer, for example, polyethyleneimine, an ionic polymer complex composed of a polymer having polyethyleneimine and a carboxylic acid, a primary amine-grafted acrylic resin in which a primary amine is grafted on an acrylic main skeleton, polyallylamine, or Examples thereof include aminophenols and derivatives thereof. These cationic polymers may be used individually by 1 type, and may be used in combination of 2 or more type. Examples of the crosslinking agent include compounds having at least one functional group selected from the group consisting of isocyanate groups, glycidyl groups, carboxyl groups, and oxazoline groups, silane coupling agents, and the like. These crosslinking agents may be used alone or in combination of two or more.

  These chemical conversion treatments may be performed alone or in combination of two or more chemical conversion treatments. Furthermore, these chemical conversion treatments may be carried out using one kind of compound alone, or may be carried out using a combination of two or more kinds of compounds. Among these, chromic acid chromate treatment is preferable, and chromate treatment in which a chromic acid compound, a phosphoric acid compound, and an aminated phenol polymer are combined is more preferable.

The amount of the acid-resistant film formed on the surface of the metal layer 3 in the chemical conversion treatment is not particularly limited. For example, if the chromate treatment is performed by combining a chromic acid compound, a phosphoric acid compound, and an aminated phenol polymer. The chromic acid compound is about 0.5 to about 50 mg, preferably about 1.0 to about 40 mg in terms of chromium, and the phosphorus compound is about 0.5 to about 50 mg in terms of phosphorus per 1 m ² of the surface of the metal layer 3. Is preferably about 1.0 to about 40 mg, and about 1 to about 200 mg, preferably about 5.0 to 150 mg of aminated phenol polymer.

  In the chemical conversion treatment, a solution containing a compound used for forming an acid-resistant film is applied to the surface of the metal layer 3 by a bar coating method, a roll coating method, a gravure coating method, a dipping method or the like, and then the temperature of the metal layer 3 is reached. Is performed by heating so as to be about 70 to 200 ° C. In addition, before the chemical conversion treatment is performed on the metal layer 3, the metal layer 3 may be subjected to a degreasing treatment by an alkali dipping method, an electrolytic cleaning method, an acid cleaning method, an electrolytic acid cleaning method, or the like in advance. By performing the degreasing treatment in this way, it becomes possible to more efficiently perform the chemical conversion treatment on the surface of the metal layer 3.

[Sealant layer 4]
In the battery packaging material, the sealant layer 4 corresponds to the innermost layer, and is a layer that seals the battery element by heat-sealing the sealant layers when the battery is assembled.

  The resin component used for the sealant layer 4 is not particularly limited as long as it can be thermally welded, and examples thereof include polyolefin, cyclic polyolefin, carboxylic acid-modified polyolefin, and carboxylic acid-modified cyclic polyolefin.

  Specific examples of the polyolefin include polyethylene such as low density polyethylene, medium density polyethylene, high density polyethylene, and linear low density polyethylene; homopolypropylene, polypropylene block copolymer (for example, block copolymer of propylene and ethylene), polypropylene And a random copolymer (for example, a random copolymer of propylene and ethylene); an ethylene-butene-propylene terpolymer; and the like. Among these polyolefins, polyethylene and polypropylene are preferable.

  The cyclic polyolefin is a copolymer of an olefin and a cyclic monomer, and examples of the olefin that is a constituent monomer of the cyclic polyolefin include ethylene, propylene, 4-methyl-1-pentene, styrene, butadiene, and isoprene. Is mentioned. Examples of the cyclic monomer that is a constituent monomer of the cyclic polyolefin include cyclic alkenes such as norbornene; specifically, cyclic dienes such as cyclopentadiene, dicyclopentadiene, cyclohexadiene, and norbornadiene. Among these polyolefins, cyclic alkene is preferable, and norbornene is more preferable.

  The carboxylic acid-modified polyolefin is a polymer obtained by modifying the polyolefin by block polymerization or graft polymerization with carboxylic acid. Examples of the carboxylic acid used for modification include maleic acid, acrylic acid, itaconic acid, crotonic acid, maleic anhydride, itaconic anhydride and the like.

  The carboxylic acid-modified cyclic polyolefin is obtained by copolymerizing a part of the monomer constituting the cyclic polyolefin in place of the α, β-unsaturated carboxylic acid or its anhydride, or α, β with respect to the cyclic polyolefin. -A polymer obtained by block polymerization or graft polymerization of an unsaturated carboxylic acid or its anhydride. The cyclic polyolefin to be modified with carboxylic acid is the same as described above. The carboxylic acid used for modification is the same as that used for modification of the acid-modified cycloolefin copolymer.

  Among these resin components, carboxylic acid-modified polyolefin is preferable; carboxylic acid-modified polypropylene is more preferable.

  The sealant layer 4 may be formed of one kind of resin component alone, or may be formed of a blend polymer in which two or more kinds of resin components are combined. Furthermore, the sealant layer 4 may be formed of only one layer, but may be formed of two or more layers using the same or different resin components.

  In the battery packaging material, the sealant layer 4 may contain a lubricant. The type of lubricant is not particularly limited, and examples thereof include those exemplified in the above item [Base Material Layer 1]. When the sealant layer 4 contains a lubricant, the content thereof may be selected as appropriate, but preferably about 700 to 1200 ppm, more preferably about 800 to 1100 ppm. In the present invention, the content of the lubricant in the sealant layer 4 is the total amount of the lubricant present in the sealant layer 4 and the lubricant present on the surface of the sealant layer 4.

  The thickness of the sealant layer 4 can be selected as appropriate, and is about 10 to 100 μm, preferably about 15 to 50 μm.

[Adhesive layer 5]
In the battery packaging material, the adhesive layer 5 is a layer provided between the metal layer 3 and the sealant layer 4 as necessary in order to firmly bond the metal layer 3 and the sealant layer 4.

  The adhesive layer 5 is formed of an adhesive capable of bonding the metal layer 3 and the sealant layer 4. With respect to the adhesive used for forming the adhesive layer 5, the adhesive mechanism, the types of adhesive components, and the like are the same as those of the adhesive layer 2. The adhesive component used for the adhesive layer 5 is preferably a polyolefin resin, more preferably a carboxylic acid-modified polyolefin, particularly preferably a carboxylic acid-modified polypropylene.

  About the thickness of the contact bonding layer 5, 2-50 micrometers, for example, Preferably 15-30 micrometers is mentioned.

Method for producing battery packaging material The method for producing the battery packaging material is not particularly limited as long as a laminate in which layers having a predetermined composition are laminated is obtained. For example, the following methods are exemplified.

  First, a laminate in which the base material layer 1, the adhesive layer 2, and the metal layer 3 are laminated in order (hereinafter also referred to as “laminate A”) is formed. Specifically, the laminate A is formed by extruding an adhesive used for forming the adhesive layer 2 on the base layer 1 or the metal layer 3 whose surface is subjected to chemical conversion treatment, if necessary. It can be performed by a dry lamination method in which the metal layer 3 or the base material layer 1 is laminated and the adhesive layer 2 is cured after being applied and dried by a coating method such as a method or a roll coating method.

  Next, the sealant layer 4 is laminated on the metal layer 3 of the laminate A. When the sealant layer 4 is directly laminated on the metal layer 3, the resin component constituting the sealant layer 4 may be applied on the metal layer 3 of the laminate A by a method such as a gravure coating method or a roll coating method. . In the case where the adhesive layer 5 is provided between the metal layer 3 and the sealant layer 4, for example, (1) the adhesive layer 5 and the sealant layer 4 are laminated on the metal layer 3 of the laminate A by coextrusion. (2) A method of separately forming a laminate in which the adhesive layer 5 and the sealant layer 4 are laminated, and laminating the laminate on the metal layer 3 of the laminate A by a thermal lamination method, 3) An adhesive for forming the adhesive layer 5 is laminated on the metal layer 3 of the laminate A by an extrusion method or a solution-coated high temperature drying and baking method, and a sheet-like shape is formed on the adhesive layer 5 in advance. (4) A melted adhesive layer 5 is placed between the metal layer 3 of the laminate A and the sealant layer 4 previously formed into a sheet shape. Adhesive layer 5 while pouring Method (sand lamination method) and the like to bond the laminate A and the sealant layer 4. In addition, in order to strengthen the adhesiveness of the adhesive layer 2 and the adhesive layer 5 provided as necessary, it may be further subjected to a heat treatment such as a hot roll contact type, a hot air type, a near or far infrared type. Examples of such heat treatment conditions include 150 to 250 ° C. for 1 to 5 minutes.

  In the battery packaging material, each layer constituting the laminate is improved or stabilized as necessary, for example, film forming property, lamination processing, final product secondary processing (pouching, embossing) suitability, etc. Surface activation treatment such as corona treatment, blast treatment, oxidation treatment, and ozone treatment may be performed.

Application of battery packaging material molded body The battery packaging material molded body of the present invention is used as a packaging material for sealing and housing battery elements such as a positive electrode, a negative electrode, and an electrolyte.

  Specifically, a battery element including at least a positive electrode, a negative electrode, and an electrolyte is formed in the battery packaging material molded body of the present invention, with metal terminals connected to each of the positive electrode and the negative electrode protruding outward. By covering the periphery of the battery element so that a flange portion (region where the sealant layers contact each other) can be formed, and sealing the sealant layers of the flange portion by heat sealing, Used batteries are provided. In addition, when accommodating a battery element using the battery packaging material molded body of the present invention, the battery packaging material is used such that the sealant portion is on the inner side (surface in contact with the battery element).

  Since the battery packaging material molded body of the present invention is used in the battery of the present invention, the ink is suitably printed on the surface of the battery after the battery packaging material is molded and the battery element is sealed. can do. That is, for example, the ink can be suitably printed by pad printing in which the ink is likely to be repelled in the base material layer having a lubricant on the surface, and at least a part of the surface of the battery, for example, a barcode, a handle, Printing of characters and the like can be suitably formed.

  The molded article for battery packaging material of the present invention may be used for either a primary battery or a secondary battery, but is preferably a secondary battery. The type of the secondary battery to which the battery packaging material molded body of the present invention is applied is not particularly limited. For example, a lithium ion battery, a lithium ion polymer battery, a lead live battery, a nickel / hydrogen live battery, nickel / cadmium Examples include livestock batteries, nickel / iron livestock batteries, nickel / zinc livestock batteries, silver oxide / zinc livestock batteries, metal-air batteries, multivalent cation batteries, capacitors, capacitors, and the like. Among these secondary batteries, lithium ion batteries and lithium ion polymer batteries can be cited as suitable applications of the battery packaging material molded body of the present invention.

  Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples. However, the present invention is not limited to the examples.

Example 1 and Comparative Example 1
<Manufacture of battery packaging material moldings>
On a base material layer (thickness 15 μm) made of nylon resin, a metal layer made of aluminum foil (thickness 35 μm) subjected to chemical conversion treatment on both surfaces was laminated by a dry lamination method. Specifically, a two-component urethane adhesive (a polyol compound and an aromatic isocyanate compound) was applied to one surface of an aluminum foil, and an adhesive layer (thickness 3 μm) was formed on the metal layer. Next, the adhesive layer on the metal layer and the base material layer were dry-laminated to form a base material layer / adhesive layer / metal layer laminate. In addition, the chemical conversion treatment of the aluminum foil used as the metal layer is performed by roll coating a treatment liquid composed of a phenol resin, a chromium fluoride compound, and phosphoric acid so that the coating amount of chromium is 10 mg / m ² (dry weight). The coating was performed on both surfaces of the aluminum foil by the method and baked for 20 seconds under the condition that the film temperature was 180 ° C. or higher. Next, 20 μm of carboxylic acid-modified polypropylene (arranged on the metal layer side) and 20 μm of random polypropylene (innermost layer) are co-extruded on the metal layer of the laminate, whereby an adhesive layer / thermoadhesive resin layer is formed on the metal layer. Were laminated. In addition, 700 ppm of erucic acid amide was added to the random polypropylene as a lubricant. The battery packaging material was obtained through the above steps.

[Molding process]
Each battery packaging material obtained above was cut into a rectangle of 80 mm × 120 mm to prepare a sample. This sample is cold-molded using a molding die (female) having a diameter of 30 × 50 mm and a corresponding molding die (male) under the conditions of a pressing pressure of 0.4 MPa and a molding depth of 6 mm. As a result, a battery packaging material molded body was obtained.

In addition, about the sample after cold forming, the deepest shaping | molding depth which does not generate | occur | produce a pinhole and a crack in all ten samples about a wrinkle or aluminum foil was made into the limit shaping | molding depth of the sample. From this limit molding depth, the moldability of the battery packaging material was evaluated according to the following criteria. The results are shown in Table 1.
○: Limit forming depth 6.8 mm or more ×: Limit forming depth mm or less

[Surface modification process]
Using the quartz electrode corona surface treatment device manufactured by Kasuga Denki Co., Ltd., the surface of the base material layer 1 of each of the battery packaging material molded bodies obtained above under the conditions of 3 Kw output and 30 MT / min constant speed A part of the sample was irradiated with corona discharge. The corona treatment was performed only on the battery packaging material molded body of Example 1, and not on the battery packaging material molded body of Comparative Example 1.

[Evaluation method of ink printing characteristics]
Ink printing characteristics were obtained by pad printing on the surface-modified portion of the battery packaging material molded body of Example 1 and the base material layer surface of the battery packaging material molded body of Comparative Example 1, respectively. Evaluated. The pad printer used was SPACE PAD 6GX manufactured by Mishima Corporation. Further, TBP980 black / H2 curing agent / TPV solvent manufactured by Marabu was used as the ink. The printed ink was cured at 80 ° C. for 10 minutes. The printed surface after curing was observed with an optical microscope, and the printing characteristics of the ink were evaluated according to the following criteria. Ink printing was performed in an environment of 24 ° C. and a relative humidity of 50%. The results are shown in Table 1.
○: Print missing is within 5% of the entire printed pattern Δ: Printing missing is more than 40% of the entire printed pattern x: Printing missing is more than 80% of the entire printed pattern

(Evaluation of printing characteristics of ink after winding)
Each battery packaging material obtained in Example 1 and Comparative Example 1 is wound up, stored at 5 ° C. for 30 days, or stored at 40 ° C. for 30 days, and then the molding step and surface modification step in the same manner as described above. In the same manner, the printing characteristics of the ink were evaluated. The results are shown in Table 1.

[Measurement of surface tension]
About the part which performed the surface modification process of the packaging material molding for batteries of Example 1, and the base material layer surface of the packaging material molding for batteries of Comparative Example 1, the surface was formed by a method based on the provisions of JIS K6768: 1999. Tension was measured. For the purpose of comparative verification of printing suitability, surface tension value determination using a wetting reagent in accordance with JIS K6768: 1999 was performed. Using a liquid mixture for wetting tension test manufactured by Nacalai Tesque, apply the reagent contained in a cotton swab in a line of about 10 cm, and visually determine whether the liquid film is broken after 3 seconds. The tension value was defined as the surface tension of the substrate. The surface tension was measured in an environment at 24 ° C. and a relative humidity of 50%. The results are shown in Table 1.

DESCRIPTION OF SYMBOLS 1 Base material layer 2 Adhesive layer 3 Metal layer 4 Sealant layer 5 Adhesive layer 10 Battery packaging material 11 Battery packaging material molding

Claims (11)

At least a step of preparing a battery packaging material in which a base material layer, a metal layer, and a sealant layer are sequentially laminated;
A molding step of cold-molding the battery packaging material;
Before or after the molding step, a surface modification step for surface-modifying the outer surface of the base material layer of the battery packaging material;
Equipped with a,
The manufacturing method of the packaging material molded object for batteries which performs the said surface modification process after the said shaping | molding process .   At least a step of preparing a battery packaging material in which a base material layer, a metal layer, and a sealant layer are sequentially laminated;
  A molding step of cold-molding the battery packaging material;
  Before or after the molding step, a surface modification step for surface-modifying the outer surface of the base material layer of the battery packaging material;
With
  The manufacturing method of the battery packaging material molding which performs the said surface modification process only to a part of outer surface of the said base material layer of the said battery packaging material.   At least a step of preparing a battery packaging material in which a base material layer, a metal layer, and a sealant layer are sequentially laminated;
  A molding step of cold-molding the battery packaging material;
  Before or after the molding step, a surface modification step for surface-modifying the outer surface of the base material layer of the battery packaging material;
With
  After the surface modification step, further comprising a printing step of printing ink on the outer surface of the base material layer,
  The manufacturing method of the packaging material molded object for batteries which performs the said printing process by pad printing.   The method for producing a molded article for battery packaging material according to claim 2 or 3, wherein the surface modification step is performed after the molding step.   The manufacturing method of the battery packaging material molded object of Claim 1 or 3 which performs the said surface modification process only to a part of outer surface of the said base material layer of the said battery packaging material.   The manufacturing method of the packaging material molded object for batteries of Claim 1 or 2 further equipped with the printing process which prints an ink on the outer surface of the said base material layer after the said surface modification process.   The manufacturing method of the packaging material molded object for batteries of Claim 6 which performs the said printing process by pad printing. The manufacturing method of the packaging material molded object for batteries in any one of Claims 1-7 whose said surface modification process is a corona treatment. A battery packaging material winding body is prepared as the battery packaging material, and the molding process is performed by cutting the battery packaging material unwound from the winding body into a predetermined size. method of manufacturing a battery packaging material molded body according to any one of 1-8. The lubricant on the surface of the substrate layer is present, the manufacturing method for a battery packaging material molded body according to any one of claims 1-9. The method for producing a molded article for battery packaging material according to any one of claims 1 to 10 , wherein the surface tension of the portion modified by the surface modification treatment is 35 mN / m or more.