JP2022047475A - Aluminum foil, method for producing the same and use thereof - Google Patents

Abstract

To provide aluminum foil that has sufficient moldability and flexibility required for a soft pack of a lithium ion battery.SOLUTION: This aluminum foil contains, in mass%, Fe: 0.7-2.0 wt.%, Si: 0.02-0.9 wt.%, Cu: 0.5 wt.% or less, Mg: 0.1 wt.% or less, Mn: 0.7 wt.% or less, Zn: 0.05 wt.% or less, Cr: 0.05 wt.% or less, Ti: 0.1 wt.% or less, and V: 0.05 wt.% or less, with the balance being Al and unavoidable impurities. The cubic texture has a volume fraction of 5-20%, and the average surface grain size is 5-35 μm.SELECTED DRAWING: None

Description

The present invention relates to packaging materials, especially aluminum foil. Furthermore, the present invention relates to a method for producing the aluminum foil, a packaging material for a soft pack lithium ion battery containing the aluminum foil, and a soft pack lithium ion battery.

With the rapid development of science and technology, the market demand for aluminum alloys is also growing rapidly. Aluminum alloys are widely used in fields such as aerospace, telecommunications, military industry, medicine, and machine manufacturing. Of these, aluminum foil occupies an important position in the use of aluminum alloys. Aluminum foil itself is lightweight, has strong barrier performance, high ductility, excellent molding performance, and is widely used in industries such as packaging, electronic products, electrical products, and construction.

Aluminum laminating film, which is an aluminum foil for soft-pack lithium-ion batteries, is attracting attention in the packaging field. In order to ensure the safety and durability of the lithium-ion battery, there are very high demands on the aluminum laminated film and each major material (particularly aluminum foil) for manufacturing the film. The aluminum-plastic film must first be stamped and molded in use, then the battery cell must be inserted and heat-sealed, and then the heat-sealed edges must be folded 2-3 times at 180 °. In this process, if the aluminum foil is not flexible, the aluminum foil is prone to cracking, damaging the heat seal layer, causing leakage and expansion of the battery, and prone to safety accidents.

In the prior art, there are many studies on the flexibility of paper and cloth, such as characterization methods and influence mechanisms. CN109295346A discloses a highly conductive flexible aluminum alloy and its manufacturing method and application, and by adjusting the alloy composition and processing method, a highly conductive flexible aluminum alloy can be obtained. However, the disclosed alloy composition and manufacturing method are not suitable for soft pack aluminum foil and its manufacturing.

According to the inventor of the present invention, aluminum foil is an important material for the intermediate layer of the aluminum laminated film, and its molding performance is significantly lower than that of the outer nylon and inner polypropylene materials, and thus the molding performance of the aluminum foil. We have found that improvement is the key to improving the molding performance of aluminum plastic films. Furthermore, the inventor of the present invention has found that the smaller the size of the crystal grains of the aluminum foil, the more adversely the improvement of the flexibility is adversely affected, and the harder the material is. Therefore, the inventor of the present invention has conducted diligent research in view of the requirements for molding performance and flexibility of soft-packed aluminum foil for lithium-ion batteries and the current state of the industry. We discovered that (crystal grain size) affects the flexibility and molding performance of the aluminum foil, which is a product, and by controlling the texture of the aluminum foil and the size of the crystal grains, the flexibility and molding performance of the aluminum foil. Was able to be achieved and the present invention was completed.

Specifically, the present invention relates to the following aspects.

1. 1. Fe: 0.7-2.0 wt% (preferably 0.7-1.7 wt%, more preferably 1.0-1.5 wt%), Si: 0.02-0.9 wt% (preferably 0.7-1.5 wt%) by mass% Preferably 0.05-0.1 wt%, more preferably 0.05-0.08 wt%), Cu: 0.5 wt% or less (preferably 0.001-0.5 wt%, preferably 0.05 wt% or less) , More preferably 0.0015-0.05 wt%), Mg: 0.1 wt% or less (preferably 0.001-0.1 wt%, preferably 0.05 wt% or less, more preferably 0.001-0. 008 wt%), Mn: 0.7 wt% or less (preferably 0.005-0.7 wt%, preferably 0.05 wt% or less, more preferably 0.007-0.04 wt%), Zn: 0.05 wt% Below (preferably 0.001-0.03 wt%, more preferably 0.01-0.02 wt%), Cr: 0.05 wt% or less (preferably 0.0005-0.05 wt%, preferably 0.005 wt%) % Or less, more preferably 0.0007-0.002 wt%), Ti: 0.1 wt% or less (preferably 0.001-0.1 wt%, preferably 0.02 wt% or less, more preferably 0.007- 0.02 wt%), V: 0.05 wt% or less (preferably 0.0005-0.05 wt%, preferably 0.02 wt% or less, preferably 0.01 wt% or less, preferably 0.0005-0.01 wt) %, preferably 0.0005-0.0034 wt%, more preferably 0.009-0.0015 wt%), the balance consisting of Al and unavoidable impurities, and the body integration ratio of the cubic aggregate is 5-20% (preferably 0.0015 wt%). An aluminum foil characterized by an average surface crystal grain size of 5-35 μm (preferably 10-20 μm, more preferably 12-18 μm), 8-15%, more preferably 9-14%).

2. 2. The flexibility of the aluminum foil is 450 mN or less (preferably 330-450 mN, more preferably 340-420 mN, more preferably 350-395 mN), and the Eriksen value of the aluminum foil is 5.0 mm or more (preferably 5.0). -10.0 mm, more preferably 6.0-9.0 mm, more preferably 7.0-8.0 mm)) according to any of the above or below forms of the aluminum foil.

3. 3. Intermediate annealing step: An aluminum foil material (preferably 0.1-2.0 mm thick, more preferably 0.3-1.0 mm thick) is intermediately annealed to obtain an annealed aluminum foil material.
Rolling process: The annealed aluminum foil material is rolled to obtain an aluminum foil (also called a semi-finished aluminum foil), and the final annealing step: The semi-finished aluminum foil is finally annealed to obtain an aluminum foil (also called a finished aluminum foil). With the process of getting (called),
The intermediate annealing step includes at least an annealing step A1, the annealing temperature of the annealing step A1 (referred to as annealing temperature A1) is 300-395 ° C (preferably 340-380 ° C), and the final annealing step is at least an annealing step. The annealing step B2 after the annealing step B1 is included, and the annealing temperature (referred to as the annealing temperature B1) of the annealing step B1 is 70-150 ° C (preferably 90-140 ° C), and the annealing step B2. A method for producing an aluminum foil, characterized in that the annealing temperature (referred to as annealing temperature B2) is 220-350 ° C (preferably 250-300 ° C or 250-280 ° C).

4. The annealing temperature A1 is 50-150 ° C higher (preferably 70-100 ° C higher) than the annealing temperature B2, and / or the annealing temperature B2 is 80-200 ° C higher (preferably 105) than the annealing temperature B1. -185 ° C higher) The production method according to any of the above or below.

5. The intermediate annealing step includes at least keeping the aluminum foil material at a temperature of 300-400 ° C. (preferably 340-380 ° C.) (annealing temperature A1), or at least the aluminum foil material at 150-180 ° C. The production method according to any one of the above or below, which comprises a step of keeping the temperature at 300-400 ° C (preferably 340-380 ° C) (annealing temperature A1).

6. The rolling step includes a step of rough rolling, intermediate rolling, and finish rolling of the annealed aluminum foil material, and in the rough rolling, the annealed aluminum foil material is preferably 0.2-0.5 mm thick (preferably). Is rolled into a roll material having a thickness of 0.1-0.3 mm), and in the intermediate rolling, the roll material has a thickness of 0.05-0.2 mm (preferably 0.07-0.1 mm). Rolled into an aluminum foil, and in the finish rolling, the aluminum foil is 0.025-0.06 mm thick (preferably 0.03-0.05 mm thick, more preferably 0.035-0.045 mm thick). The production method according to any one of the above or below, which is rolled into an aluminum foil (that is, the semi-finished aluminum foil).

7. In the final annealing step, the temperature is kept at a temperature of at least 70-150 ° C (preferably 90-140 ° C) (annealing temperature B1), and then a temperature of 220-350 ° C (preferably 250-280 ° C) (annealing temperature B2). ), Or at least 70-150 ° C (preferably 90-140 ° C) (annealing temperature B1), then 220-350 ° C (preferably 250-280 ° C). The production method according to any one of the above or below, which comprises a step of keeping the temperature at (annealing temperature B2) and then air-cooling.

8. Prior to the final annealing step, there is a split (cutting) step, in which the split stress is 25-35 MPa and / or the take-up speed is 50-150 mm / min, as described above or below. The manufacturing method according to any form.

9. The production method according to any one of the above or below, further comprising a step of subjecting an ingot of an aluminum alloy to a homogenization treatment, a hot rolling treatment and a cold rolling treatment to obtain an aluminum foil material.

10. The homogenization treatment includes at least a step of keeping the ingot of the aluminum alloy at a temperature of 550-620 ° C. (preferably 570-610 ° C.), and preferably at least the ingot of the aluminum alloy at 550-620 ° C. (preferably). The production method according to any one of the above or below, which comprises a step of keeping the temperature at 570-610 ° C. and then further keeping the temperature at 400-520 ° C. (preferably 450-510 ° C.).

11. The hot rolling process includes at least a step of rolling the homogenized aluminum alloy ingot into a 3-7 mm plate material (called a hot rolled plate material) at a temperature of at least 450 ° C., either of the above or below. The manufacturing method described in the form.

12. In the cold rolling process, at least the hot-rolled plate material is rolled into the aluminum foil material having a thickness of 0.1-2.0 mm (preferably 0.3-1.0 mm) at a temperature of 80 ° C. or lower. The production method according to any one of the above or below, which comprises a step.

13. A soft-packed lithium-ion battery comprising the aluminum foil according to any one of the above-mentioned or later forms, or the aluminum foil produced by the production method according to any one of the above-mentioned or later forms, and at least one polymer layer. Packaging material (especially aluminum laminated film for soft pack lithium-ion batteries).

14. A soft-packed lithium-ion battery comprising a positive electrode, a negative electrode, an electrolyte, a separator, and a packaging material for the soft-packed lithium-ion battery according to any one of the above or below.

According to the embodiment of the present invention, one of the following beneficial effects or a combination thereof can be realized.

(1) By optimizing the alloy composition and further controlling the fine structure and texture of the material, it is possible to produce an aluminum foil for an aluminum laminate film for a soft pack lithium ion battery having excellent flexibility.

(2) According to the composition and the manufacturing method of the present invention, it is possible to obtain a flexible aluminum foil, improve the molding performance of the aluminum foil, and comprehensively improve the flexibility and molding performance of the aluminum foil.

(3) The present invention comprehensively utilizes the heat treatment means for homogenization treatment and intermediate annealing treatment, and the plastic deformation process of hot rolling, cold rolling, and foil rolling, and has a fine chemical composition and a second phase. Effectively controls the solid dissolution and precipitation morphology of the material in the aluminum matrix, and further performs the annealing process in two stages to realize the structure of fine equiaxed recrystallized grains and the fraction of the recrystallized cubic aggregate structure in a certain ratio. However, the optimum harmony between the molding performance of the aluminum foil and the flexibility can be realized.

(4) By controlling the process parameters related to the splitting process before the final annealing process, the cleanliness of the surface of the aluminum foil can be significantly improved, and the packaging material of the soft pack lithium ion battery and the soft pack lithium ion battery can be improved. Especially suitable for.

Hereinafter, the present invention will be invented in more detail with reference to specific embodiments. However, it should be noted that the scope of protection of the present invention should not be construed as limited to these specific embodiments, but rather should be determined by the appended claims.

All publications, patent applications, patents and other literature described herein are hereby incorporated by reference in their entirety. Moreover, unless otherwise defined, all technical and scientific terms used herein have the same meanings generally as understood by one of ordinary skill in the art to which the invention belongs. In the event of inconsistency, the definitions herein shall prevail.

Where "known to those skilled in the art" or "in the art" or similar terms herein are used to describe materials, materials, methods, processes, devices or equipment, etc., are recognized in the art. As used, the term is not only used in the art at the time this application was filed, but is not yet commonly used, but is a definition that seeks to be appropriate for similar purposes. Also includes.

In the present specification, so-called "substantially" is acceptable to those skilled in the art, such as deviations within ± 10%, within ± 5%, within ± 1%, within ± 0.5% or within ± 0.1%. Refers to a reasonable deviation.

In the present specification, unless otherwise specified, temperature generally refers to the temperature of the material itself during heat treatment (annealing, homogenization, or hot rolling).

In the present specification, unless otherwise specified, percentages, parts, ratios, ratios, etc. are all based on weight. And the pressure is the gauge pressure.

In the present specification, any two or more forms of the present invention can be arbitrarily combined, and the forms formed thereby belong to a part of the original disclosure contents of the present specification, and the scope of protection of the present invention. Is also included.

One embodiment of the invention provides aluminum foil. The aluminum foil can realize the optimum harmony between the molding performance and the flexibility of the aluminum foil, and is particularly applied to an aluminum laminating film for a soft pack lithium ion battery.

According to one embodiment of the present invention, the thickness of the aluminum foil is not particularly limited, but is generally 25-60 μm, preferably 30-50 μm, and more preferably 35-45 μm.

According to one embodiment of the present invention, the aluminum foil is in mass%, Fe is generally 0.7-2.0 wt%, preferably 0.7-1.7 wt%, more preferably 1.0-1. Included at .5 wt%.

According to one embodiment of the present invention, the aluminum foil is in mass%, Si is generally 0.02-0.9 wt%, preferably 0.05-0.1 wt%, more preferably 0.05-0. Included at .08 wt%.

According to one embodiment of the present invention, the aluminum foil contains Cu in a mass% of 0.5 wt% or less, preferably 0.001-0.5 wt%, preferably 0.05 wt% or less, more preferably. Included at 0.0015-0.05 wt%.

According to one embodiment of the present invention, the aluminum foil contains Mg in a mass% of generally 0.1 wt% or less, preferably 0.001-0.1 wt%, preferably 0.05 wt% or less, more preferably. Included at 0.001-0.008 wt%.

According to one embodiment of the present invention, the aluminum foil has an Mn content of generally 0.7 wt% or less, preferably 0.005-0.7 wt%, preferably 0.05 wt% or less, more preferably 0.05 wt% or less in mass%. Included at 0.007-0.04 wt%.

According to one embodiment of the present invention, the aluminum foil has a mass% of Zn, generally 0.05 wt% or less, preferably 0.001-0.03 wt%, and more preferably 0.01-0.02 wt%. Including in.

According to one embodiment of the present invention, the aluminum foil is generally 0.05 wt% or less, preferably 0.0005-0.05 wt%, preferably 0.005 wt% or less, more preferably Cr in% by mass. Included at 0.0007-0.002 wt%.

According to one embodiment of the present invention, the aluminum foil is generally 0.1 wt% or less, preferably 0.001-0.1 wt%, preferably 0.02 wt% or less, more preferably Ti in% by mass. Included at 0.007-0.02 wt%.

According to one embodiment of the present invention, the aluminum foil has a V of generally 0.05 wt% or less, preferably 0.0005-0.05 wt%, preferably 0.02 wt% or less, preferably 0 in mass%. It is contained in an amount of 0.01 wt% or less, preferably 0.0005-0.01 wt%, preferably 0.0005-0.0034 wt%, and more preferably 0.009-0.0015 wt%.

According to one embodiment of the present invention, the aluminum foil has the balance of Al and unavoidable impurities.

According to one embodiment of the present invention, the aluminum foil has a volume fraction of the cubic texture generally 5-20%, preferably 8-15%, more preferably 9-14%. Here, the volume fraction of the cubic aggregate structure is measured by the method described in the examples.

According to one embodiment of the present invention, the aluminum foil has an average surface crystal grain size of generally 5-35 μm, preferably 10-20 μm, and more preferably 12-18 μm. Here, the size of the average surface crystal grains is measured by the method described in the examples.

According to one embodiment of the present invention, the aluminum foil has a flexibility of generally 450 mN or less, preferably 330-450 mN, more preferably 340-420 mN, and more preferably 350-395 mN. Here, the flexibility is measured by the method described in the examples.

According to one embodiment of the present invention, the aluminum foil generally has an Eriksen value of 5.0 mm or more, preferably 5.0-10.0 mm, more preferably 6.0-9.0 mm, and more preferably. Is 7.0-8.0 mm. Here, the Eriksen value is measured by the method described in the examples.

According to one embodiment of the present invention, the aluminum foil can be manufactured by the following manufacturing method (referred to as a manufacturing method of aluminum foil).

According to one embodiment of the present invention, the method for manufacturing an aluminum foil includes the following steps.
Intermediate annealing process: The aluminum foil material is intermediately annealed to obtain the annealed aluminum foil material.
Rolling process: The annealed aluminum foil material is rolled to obtain an aluminum foil (also called a semi-finished aluminum foil), and the final annealing step: The semi-finished aluminum foil is finally annealed to obtain an aluminum foil (also called a finished aluminum foil). Called).

According to one embodiment of the present invention, in the method for producing an aluminum foil, the aluminum foil material is preferably 0.1-2.0 mm thick, more preferably, from the viewpoint of the effect of the best technique of the present invention. Is 0.3-1.0 mm thick.

According to one embodiment of the present invention, in the method for producing an aluminum foil, the intermediate annealing step includes at least an annealing step A1, and the annealing temperature (referred to as annealing temperature A1) of the annealing step A1 is generally 300-395 ° C. The temperature is preferably 340-380 ° C.

According to one embodiment of the present invention, in the method for producing an aluminum foil, the final annealing step includes at least an annealing step B1 and an annealing step B2 after the annealing step B1. Here, the annealing temperature (referred to as annealing temperature B1) in the annealing step B1 is generally 70-150 ° C, preferably 90-140 ° C. The annealing temperature (referred to as annealing temperature B2) in the annealing step B2 is generally 220-350 ° C, preferably 250-300 ° C or 250-280 ° C.

According to one embodiment of the present invention, in the method for producing an aluminum foil, the annealing temperature A1 is 50-150 ° C. higher than the annealing step B2, preferably 70-, from the viewpoint of the effect of the best technique of the present invention. 100 ° C higher.

According to one embodiment of the present invention, in the method for producing an aluminum foil, the annealing temperature B2 is 80-200 ° C. higher than the annealing step B1, preferably 105-, in terms of the effect of the best technique of the present invention. It is 185 ° C higher.

According to one embodiment of the present invention, in the method for producing an aluminum foil, at least the aluminum foil material is kept at a temperature of 300-400 ° C. (preferably 340-380 ° C.) (annealing temperature A1) in the intermediate annealing step. do. The heat retention time is generally at least 2 hours, preferably 2-10 hours.

According to another embodiment of the present invention, in the method for producing an aluminum foil, at least the aluminum foil material is kept at a temperature of 150-180 ° C. in the intermediate annealing step. The heat retention time is generally at least 2 hours, preferably 2-5 hours. Further, after that, the temperature is kept at a temperature of 300-400 ° C (preferably 340-380 ° C) (annealing temperature A1). The heat retention time is generally at least 2 hours, preferably 2-10 hours.

According to one embodiment of the present invention, in the method for manufacturing aluminum foil, the rolling step includes a step of rough rolling, intermediate rolling, and finish rolling of an annealed aluminum foil material.

According to one embodiment of the present invention, in the rolling step, in the rough rolling, the annealed aluminum foil material is rolled into a roll having a thickness of 0.2-0.5 mm (preferably a thickness of 0.1-0.3 mm). Roll into wood.

According to one embodiment of the present invention, in the rolling step, in the intermediate rolling, the roll material is made into an aluminum foil having a thickness of 0.05-0.2 mm (preferably 0.07-0.1 mm). Roll.

According to one embodiment of the present invention, in the rolling step, in the finish rolling, the aluminum foil has a thickness of 0.025-0.06 mm (preferably a thickness of 0.03-0.05 mm, more preferably a thickness). It is rolled into an aluminum foil (that is, the semi-finished aluminum foil) having a size of 0.035 to 0.045 mm. The semi-finished aluminum foil is generally in the form of a roll material.

According to one embodiment of the present invention, in the method for producing an aluminum foil, the aluminum foil is kept at a temperature of at least 70-150 ° C. (preferably 90-140 ° C.) (annealing temperature B1) in the final annealing step. The heat retention time is generally at least 10 hours, preferably 10-40 hours. Further, after that, the temperature is kept at a temperature of 200-350 ° C. (preferably 250-280 ° C.) (annealing temperature B2). The heat retention time is generally at least 20 hours, preferably 30-90 hours.

According to another embodiment of the present invention, in the method for producing an aluminum foil, the temperature is kept at at least 70-150 ° C. (preferably 90-140 ° C.) (annealing temperature B1) in the final annealing step. The heat retention time is generally at least 10 hours, preferably 10-40 hours. Further, after that, the temperature is kept at a temperature of 200-350 ° C. (preferably 250-280 ° C.) (annealing temperature B2). The heat retention time is generally at least 20 hours, preferably 30-90 hours. Then air cool.

According to one embodiment of the present invention, the semi-finished aluminum foil is divided (divided step) before final annealing. In the present specification, the divided semi-finished aluminum foil is also simply referred to as semi-finished aluminum foil. Here, the final annealing step may be a step of applying the semi-finished aluminum foil before the division, or may be a step of applying the semi-finished aluminum foil after the division.

According to one embodiment of the present invention, in the above-mentioned division, rolled (particularly finish-rolled) aluminum foil (also referred to as a large coil of aluminum foil) is divided in the vertical direction and the horizontal direction by a dividing machine, and the length and width are obtained. Divide into small rolls of different aluminum foil. Generally, the divided small rolls have a width of 1 / 2-1 / 6 of a large coil and a length of an integral multiple of 2000 meters, but may not be limited thereto. In the case of splitting, the splitting force applied to the surface of the aluminum foil is the splitting stress multiplied by the width of the small roll and the thickness of the aluminum foil.

According to one embodiment of the present invention, in the above division, the division stress is generally 25 to 35 MPa from the viewpoint of improving the surface cleanliness of the aluminum foil. In the present specification, the surface cleanliness is expressed by the amount of oil remaining on the surface of the aluminum foil. Therefore, the smaller the amount of residual rolling oil, the higher the cleanliness. A method for measuring the amount of residual rolling oil on the surface of the aluminum foil is shown in Examples.

According to one embodiment of the present invention, in the above division, the winding speed (winding speed of a small roll) is generally 50 to 150 mm / min from the viewpoint of improving the surface cleanliness of the aluminum foil.

According to one embodiment of the present invention, in the method for producing an aluminum foil, an ingot of an aluminum alloy is subjected to a homogenization treatment, a hot rolling treatment, and a cold rolling treatment to obtain an aluminum foil material.

According to one embodiment of the present invention, in the method for producing an aluminum foil, at least the ingot of an aluminum alloy is kept at a temperature of 550-620 ° C (preferably 570-610 ° C) in the homogenization treatment. The heat retention time is generally at least 6 hours, preferably 6-20 hours. Preferably, in the homogenization treatment, at least the ingot of the aluminum alloy is kept at a temperature of 550-620 ° C (preferably 570-610 ° C). The heat retention time is generally at least 6 hours, preferably 6-20 hours. Next, the temperature is kept at a temperature of 400-520 ° C (preferably 450-510 ° C). The heat retention time is generally at least 2 hours, preferably 2-10 hours.

According to one embodiment of the present invention, in the method for producing an aluminum foil, in the hot rolling process, at least a homogenized ingot of an aluminum alloy is rolled into a 3-7 mm plate material (hot rolling) at a temperature of at least 450 ° C. Roll into a plate (called a plate).

According to one embodiment of the present invention, in the hot rolling process, a homogenized aluminum alloy ingot is rolled into a 1 + N (N ≧ 1) continuous hot rolling apparatus with a deformation amount of 25-60% per pass. Hot roll.

According to one embodiment of the present invention, in the hot rolling process, the surface roughness of the roll is 0.63-1.25 μm.

According to one embodiment of the present invention, in the hot rolling process, an aqueous emulsion having a pH value of 7 or more (preferably 7-8.5) at 45-65 ° C. is used for lubrication and cooling during rolling. ..

According to one embodiment of the present invention, in the hot rolling process, after the rolling is completed, the hot rolled plate material is wound at a temperature of 250 ° C. or higher and cooled at room temperature.

According to one embodiment of the present invention, in the method for producing an aluminum foil, in the cold rolling process, at least the hot rolled plate material is heated to a temperature of 80 ° C. or lower (for example, room temperature) and has a thickness of 0.1-. Roll to the aluminum foil material of 2.0 mm (preferably 0.3-1.0 mm thick).

According to one embodiment of the present invention, in the cold rolling process, cold rolling is performed at a rolling reduction rate of 20-60% per pass.

According to one embodiment of the present invention, the cold rolling treatment contains 95% or more of 80-100 # kerosene as a base oil and 1-10% of an organic acid, alcohol or ester as an oily additive. , Filtered with diatomaceous earth and activated clay, and lubricated and cooled with 35-60 ° C. rolling oil having a light transmittance of 94% or more.

One embodiment of the present invention provides a packaging material for a soft-packed lithium-ion battery, wherein the packaging material for the soft-packed lithium-ion battery includes at least the aluminum foil of the present invention and the aluminum foil produced by the manufacturing method of the present invention. Includes one polymer layer. Conveniently, the polymer layer may be a polyolefin layer, but there are no particular restrictions. Further, at least one polymer layer and the aluminum foil can form a laminate with two or more layers.

One embodiment of the present invention provides a soft pack lithium ion battery comprising a positive electrode, a negative electrode, an electrolyte, a separator, and a packaging material for the soft pack lithium ion battery of the present invention.

According to one embodiment of the present invention, the aluminum laminate film of the lithium ion battery is used as the packaging material of the soft pack lithium ion battery. Further, as information on the packaging material of the soft pack lithium ion battery or a more specific structure or manufacturing method regarding the soft pack lithium ion battery, those known in the art can be directly applied, and there is no particular limitation. ..

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. These examples are not intended to limit the invention.

<Example 1>
The soft pack aluminum foil was manufactured from a raw material having the following composition in% by mass.

Si: 0.048%, Fe: 1.24%, Cu: 0.014%, Mn: 0.011%, Mg: 0.005%, Zn: 0.012%, Cr: 0.0007%, Ti : 0.01%, V: 0.0014%, the balance consists of Al and unavoidable impurities.

The aluminum foil was manufactured as follows.

1) Homogenization of ingots for semi-continuous casting The amount of the rectangular ingot manufactured by semi-continuous casting of the above raw materials is cut at both ends and the other four sides with a saw, and the amount cut with a saw at the ends and sides. It was homogenized at 30 mm and 15 mm, respectively, in a heating furnace at 590 ° C. for 18 hours, and further kept warm at 480 ° C. for 6 hours.

2) Hot rolling Using a 1 + 1-stage hot rolling unit equipped with a roll having a roll surface roughness of 0.63-1.25 μm under lubrication of an aqueous emulsion having a pH value of 7.5 and a temperature of 45-50 ° C. Then, the ingot at 500 ° C. was rolled. When rolled to a thickness of 4.7 mm with a deformation amount of 25-60% per pass, it was wound at 340 ° C. and cooled at room temperature.

3) Cold rolling Cold rolling was performed on an aluminum foil material of 0.5 mm at a rolling reduction of 20-60% per pass. Of these, they were lubricated and cooled with rolling oil having a light transmittance of at least 95% filtered through diatomaceous earth and / or activated clay and having a temperature of 40-45 ° C. The rolling oil contained at least 95% base oil and 5% organic acids, alcohols or esters which are oily additives.

4) Intermediate annealing In a box-type annealing furnace, the obtained aluminum foil material was kept warm at 340 ° C. for 7 hours.

5) Aluminum foil rolling The annealed 0.5 mm aluminum foil material was roughly rolled, intermediate rolled, and finished rolled to produce a 0.04 mm thick single-sided glossy aluminum foil.

6) Division of aluminum foil The division stress was controlled to be 26 MPa and the winding speed was controlled to 140 mm / min.

7) Final annealing of aluminum foil The aluminum foil was annealed in a negative pressure circulation box furnace, kept at 100 ° C. for 20 hours, further heated to 260 ° C., kept warm for 90 hours, taken out of the furnace, and air-cooled.

8) Performance measurement of aluminum foil The cubic texture of aluminum foil and the size of crystal grains were measured as follows, and the results are shown below.

First, the surface of the aluminum foil was electropolished, and then the surface of the aluminum foil was scanned in a scanning step of 2.5 μm with an EDAX model OIM2000 EBSD device equipped with a JSM6380 electron scanning electron microscope. Next, using the analytical software that came with the instrument, the cubic texture and grain size of the surface of the aluminum foil was statistic. As a result of the measurement, the aluminum foil produced in the example had a volume fraction of cubic texture of 13.5% and a crystal grain size of 12.6 μm.

The flexibility of the aluminum foil was measured as follows, and the results are shown below.

According to the method described in the national standard GB / T8942-2016 "Measurement of paper flexibility", the flexibility of the aluminum foil is measured with a tactile softness measuring device, and the maximum resistance of the measurement is defined as the flexibility of the aluminum foil. The unit was mN. The aluminum foil produced in the example had a flexibility of 355 mN.

The Eriksen value of the aluminum foil was measured as follows, and the results are shown below.

Using the GBS-60E digital display automatic cupping tester and 20 mm diameter punch, 27 mm diameter die attached to the equipment, according to the method described in National Standard GB / T4156-2007 "Metallic Materials-Ericsson Cupping Test for Thin Plates and Thin Strips". Then, the Elixin value of the aluminum foil was measured. During the measurement, the blank holder force was 10 KN, the punch speed was 10 mm / min, and the lubricant was petrolatum. The aluminum foil produced in the example had an Eriksen value of 7.8 mm.

The amount of residual oil on the surface of the aluminum foil was measured as follows, and the results are shown below.

According to the method described in Standard HJ637-2012 "Measurement of water quality, petroleum, animal and vegetable oils, infrared spectrophotometric method", the residual rolling oil on the surface of the aluminum foil sample is washed with an organic solvent, and the rolling oil in the organic solvent is carbon tetrachloride. Extracted with. After the oil was dissolved, the oil content in the solvent was measured using a NICOLET380 Fourier transform infrared spectrometer and converted into the residual oil amount per unit area. The aluminum foil produced in the example had a surface residual oil amount of 0.25 mg / m2.

<Comparative Example 1>
The procedure was the same as in Example 1 except that Fe was changed to 0.25%. As a result of the measurement, the aluminum foil produced in this comparative example had a volume fraction of a cubic texture of 22%, a crystal grain size of 26 μm, a flexibility of 280 mN, and an Elixin value of 4.8 mm.

<Comparative Example 2>
In the step 4), the same procedure as in Example 1 was carried out except that the annealing temperature was changed to 250 ° C. As a result of the measurement, the aluminum foil produced in this comparative example had a volume fraction of cubic texture of 4.5%, a crystal grain size of 13 μm, a flexibility of 460 mN, and an Elixin value of 6.5 mm.

<Comparative Example 3>
In the step 7), the aluminum foil was annealed in a negative pressure circulation box furnace, kept warm at 200 ° C. for 20 hours, further heated to 260 ° C., kept warm for 90 hours, taken out from the furnace, and air-cooled. Other than that, the same procedure as in Example 1 was performed. As a result of the measurement, the aluminum foil produced in this comparative example had a volume fraction of a cubic texture of 21%, a crystal grain size of 14.2 μm, a flexibility of 325 mN, and an Elixin value of 6.7 mm.

<Comparative Example 4>
In the step 7), the aluminum foil was annealed in a negative pressure circulation box furnace, kept warm at 100 ° C. for 20 hours, further heated to 200 ° C., kept warm for 90 hours, taken out from the furnace, and air-cooled. Other than that, the same procedure as in Example 1 was performed. As a result of the measurement, the aluminum foil produced in this comparative example had a volume fraction of a cubic texture of 4.2%, a crystal grain size of 10 μm, a flexibility of 470 mN, and an Elixin value of 6 mm.

<Comparative Example 5>
The procedure was the same as in Example 1 except that the winding speed was changed to 170 mm / min. As a result of the measurement, the aluminum foil produced in this comparative example had a surface residual oil amount of 0.40 mg / m2.

<Comparative Example 6>
The procedure was the same as in Example 1 except that the split stress was changed to 36 MPa. As a result of the measurement, the aluminum foil produced in this comparative example had a surface residual oil amount of 0.55 mg / m2.

<Comparative Example 7>
In the step 3), cold rolling was performed on a 2.5 mm aluminum foil material at a rolling reduction rate of 20-60% per pass. Other than that, the same procedure as in Example 1 was performed. As a result of the measurement, the aluminum foil produced in this comparative example had a volume fraction of cubic texture of 4.1%, a crystal grain size of 11.2 μm, a flexibility of 480 mN, and an Elixin value of 7.1 mm. rice field.

<Example 2>
The soft pack aluminum foil was manufactured from a raw material having the following composition in% by mass.

Si: 0.079%, Fe: 1.05%, Cu: 0.049%, Mn: 0.039%, Mg: 0.008%, Zn: 0.02%, Cr: 0.0016%, Ti : 0.007%, V: 0.0009%, the balance consists of Al and unavoidable impurities.

The aluminum foil was manufactured as follows.

1) Homogenization Treatment of Ingots for Semi-Continuous Casting Both ends of a rectangular ingot produced by semi-continuous casting of the above raw materials were cut with a saw, and the amount cut with a saw was 30 mm. The other four sides were two large sides and two small sides, each of which was milled and the cutting amount on one side was 15 mm. Further, the aluminum ingot was homogenized in a heating furnace at 570 ° C. for 10 hours, and further kept warm at 510 ° C. for 5 hours.

2) Hot rolling Using a 1 + 2 stage hot rolling unit equipped with a roll having a roll surface roughness of 0.63-1.25 μm, the casting at 510 ° C. with a deformation amount of 25-60% per pass. The ingot was subjected to hot rough rolling and hot finish rolling, rolled to a thickness of 5.0 mm, wound at 290 ° C., and cooled at room temperature. During rolling, an aqueous emulsion having a pH value of 7.5 and a temperature of 45-50 ° C. was used for lubrication.

3) Cold rolling Cold rolling was performed on an aluminum foil material of 0.45 mm at a rolling reduction of 20-60% per pass. Among them, the light transmittance filtered through diatomaceous earth and / or activated clay was 96%, and lubrication and cooling were performed with rolling oil having a temperature of 35-45 ° C. To ensure the smoothness and luster of the surface of the plate, the rolling oil contained at least 95% base oil and 5% organic acids, alcohols or esters which are oily additives.

4) Intermediate annealing In a box-type annealing furnace, the obtained aluminum foil material was kept warm at 370 ° C. for 4 hours.

5) Aluminum Foil Rolling An annealed 0.45 mm thick aluminum foil material was roughly rolled, intermediate rolled, and finished rolled to produce a single-sided glossy aluminum foil having a thickness of 0.035 mm.

6) Division of aluminum foil The division stress was controlled to 28 MPa and the winding speed was controlled to 100 mm / min.

7) Final annealing of single-sided glossy aluminum foil The above aluminum foil was kept warm at 80 ° C for 25 hours, heated to 300 ° C and kept warm for 60 hours, taken out of the furnace, air-cooled, and the surface residual rolling oil of the aluminum foil was removed. Then, after completely recrystallizing the fine structure of the metal, it was taken out from the furnace and air-cooled.

8) Performance measurement of aluminum foil The cubic texture of aluminum foil and the size of crystal grains were measured as follows, and the results are shown below.

First, the surface of the aluminum foil was electropolished, and then the surface of the aluminum foil was scanned in a scanning step of 2.5 μm with an EDAX model OIM2000 EBSD device equipped with a JSM6380 electron scanning electron microscope. Next, using the analytical software that came with the instrument, the cubic texture and grain size of the surface of the aluminum foil was statistic. As a result of the measurement, the aluminum foil produced in the example had a volume fraction of cubic texture of 13.5% and a crystal grain size of 17.7 μm.

The flexibility of the aluminum foil was measured as follows, and the results are shown below.

According to the method described in the national standard GB / T8942-2016 "Measurement of paper flexibility", the flexibility of the aluminum foil is measured with a tactile softness measuring device, and the maximum resistance of the measurement is defined as the flexibility of the aluminum foil. The unit was mN. The aluminum foil produced in the example had a flexibility of 354.1 mN.

The Eriksen value of the aluminum foil was measured as follows, and the results are shown below.

Using the GBS-60E digital display automatic cupping tester and 20 mm diameter punch, 27 mm diameter die attached to the equipment, according to the method described in National Standard GB / T4156-2007 "Metallic Materials-Ericsson Cupping Test for Thin Plates and Thin Strips". Then, the Elixin value of the aluminum foil was measured. During the measurement, the blank holder force was 10 KN, the punch speed was 10 mm / min, and the lubricant was petrolatum. The aluminum foil produced in the example had an Eriksen value of 7.2 mm.

The amount of residual oil on the surface of the aluminum foil was measured as follows, and the results are shown below.

According to the method described in Standard HJ637-2012 "Measurement of water quality, petroleum, animal and vegetable oils, infrared spectrophotometric method", the residual rolling oil on the surface of the aluminum foil sample is washed with an organic solvent, and the rolling oil in the organic solvent is carbon tetrachloride. Extracted with. After the oil was dissolved, the oil content in the solvent was measured using a NICOLET380 Fourier transform infrared spectrometer and converted into the residual oil amount per unit area. The aluminum foil produced in the example had a surface residual oil amount of 0.23 mg / m2.

<Example 3>
The soft pack aluminum foil was manufactured from a raw material having the following composition in% by mass.

Si: 0.066%, Fe: 1.47%, Cu: 0.0017%, Mn: 0.0072%, Mg: 0.001%, Zn: 0.0116%, Cr: 0.0008%, Ti : 0.017%, V: 0.0010%, the balance consists of Al and unavoidable impurities.

The aluminum foil was manufactured as follows.

1) Homogenization Treatment of Ingots for Semi-Continuous Casting Both ends of a rectangular ingot produced by semi-continuous casting of the above raw materials were cut with a saw, and the amount cut with a saw was 30 mm. Milling was performed on the other four side surfaces (two large side surfaces and two small side surfaces), and the cutting amount on one side was 15 mm. Further, it was homogenized at 600 ° C. for 12 hours in a heating furnace, and further kept warm at 500 ° C. for 6 hours or more.

2) Hot rolling The casting at 500 ° C. with a deformation amount of 25-60% per pass using a 1 + 4 stage hot rolling unit equipped with a roll having a roll surface roughness of 0.63-1.25 μm. The ingot was subjected to hot rough rolling and hot finish rolling, rolled to a thickness of 4.5 mm, wound at 320 ° C., and cooled at room temperature. During rolling, an aqueous emulsion having a pH value of 7.5 and a temperature of 45-50 ° C. was used for lubrication.

3) Cold rolling Cold rolling was performed on an aluminum foil material of 0.82 mm at a rolling reduction of 20-60% per pass. Among them, the light transmittance filtered through diatomaceous earth and / or activated clay was 94%, and lubrication and cooling were performed with rolling oil having a temperature of 40-45 ° C. To ensure the smoothness and luster of the surface of the plate, the rolling oil contained at least 95% base oil and 5% organic acids, alcohols or esters which are oily additives.

4) Intermediate annealing In a box-type annealing furnace, the obtained aluminum foil material was kept warm at 160 ° C. for 5 hours, then heated to 350 ° C. and kept warm for 6 hours. The metallographic structure was completely recrystallized, the hardening during cold rolling was removed, and the rolled texture was further converted into a recrystallized texture.

5) Aluminum Foil Rolling An annealed 0.82 mm thick aluminum foil material was roughly rolled, intermediate rolled, and finished rolled to produce a single-sided glossy aluminum foil having a thickness of 0.045 mm.

6) Division of aluminum foil The division stress was controlled to 28 MPa and the winding speed was controlled to 120 mm / min.

7) Final insulation of aluminum foil The aluminum foil is heated to 100 ° C in a negative pressure circulation box furnace, kept warm for 30 hours, further heated to 150 ° C and kept warm for 20 hours, and further heated to 270 ° C to keep warm for 80 hours. Then, the ratio of the crystal grain structure and the aggregated structure of the aluminum foil was adjusted, and the aluminum foil was taken out of the furnace and air-cooled.

8) Performance measurement of aluminum foil The cubic texture of aluminum foil and the size of crystal grains were measured as follows, and the results are shown below.

First, the surface of the aluminum foil was electropolished, and then the surface of the aluminum foil was scanned in a scanning step of 2.5 μm with an EDAX model OIM2000 EBSD device equipped with a JSM6380 electron scanning electron microscope. Next, using the analytical software that came with the instrument, the cubic texture and grain size of the surface of the aluminum foil was statistic. As a result of the measurement, the aluminum foil produced in the example had a volume fraction of cubic texture of 10.9% and a crystal grain size of 14.7 μm.

The flexibility of the aluminum foil was measured as follows, and the results are shown below.

According to the method described in the national standard GB / T8942-2016 "Measurement of paper flexibility", the flexibility of the aluminum foil is measured with a tactile softness measuring device, and the maximum resistance of the measurement is defined as the flexibility of the aluminum foil. The unit was mN. The aluminum foil produced in the example had a flexibility of 390.1 mN.

The Eriksen value of the aluminum foil was measured as follows, and the results are shown below.

Using the GBS-60E digital display automatic cupping tester and 20 mm diameter punch, 27 mm diameter die attached to the equipment, according to the method described in National Standard GB / T4156-2007 "Metallic Materials-Ericsson Cupping Test for Thin Plates and Thin Strips". Then, the Elixin value of the aluminum foil was measured. During the measurement, the blank holder force was 10 KN, the punch speed was 10 mm / min, and the lubricant was petrolatum. The aluminum foil produced in the example had an Eriksen value of 7.6 mm.

The amount of residual oil on the surface of the aluminum foil was measured as follows, and the results are shown below.

According to the method described in Standard HJ637-2012 "Measurement of water quality, petroleum, animal and vegetable oils, infrared spectrophotometric method", the residual rolling oil on the surface of the aluminum foil sample is washed with an organic solvent, and the rolling oil in the organic solvent is carbon tetrachloride. Extracted with. After the oil was dissolved, the oil content in the solvent was measured using a NICOLET380 Fourier transform infrared spectrometer and converted into the residual oil amount per unit area. The aluminum foil produced in the example had a surface residual oil amount of 0.28 mg / m2.

<Example 4>
The soft pack aluminum foil was manufactured from a raw material having the following composition in% by mass.

Si: 0.066%, Fe: 1.47%, Cu: 0.0017%, Mn: 0.0072%, Mg: 0.001%, Zn: 0.0116%, Cr: 0.0008%, Ti : 0.017%, V: 0.0010%, the balance consists of Al and unavoidable impurities.

The aluminum foil was manufactured as follows.

1) Homogenization Treatment of Ingots for Semi-Continuous Casting Both ends of a rectangular ingot produced by semi-continuous casting of the above raw materials were cut with a saw, and the amount cut with a saw was 30 mm. Milling was performed on the other four side surfaces (two large side surfaces and two small side surfaces), and the cutting amount on one side was 15 mm. Further, the ingot was homogenized in a heating furnace at 600 ° C. for 12 hours, and further kept warm at 490 ° C. for 8 hours.

2) Hot rolling The ingot was subjected to hot rough rolling and hot finish rolling using a 1 + 3 stage hot rolling unit equipped with a roll having a roll surface roughness of 0.63-1.25 μm. .. At the start of rolling, the ingot was rolled at a temperature of 490 ° C. and a plate material having a thickness of 4.5 mm at 320 ° C. with a deformation amount of 25-60% per pass, further wound up, and gradually cooled at room temperature. In hot rolling, in order to ensure good lubrication between the roll and the plate material, cooling action and surface quality of the plate material, an aqueous emulsion with a PH value of 7.5 and a temperature of 45-50 ° C. is used during rolling for lubrication. It was cooled.

3) Cold rolling Cold rolling was performed on an aluminum foil material of 0.56 mm at a rolling reduction rate of 20-60% per pass. Of these, they were lubricated and cooled with rolling oil having a light transmittance of at least 96% filtered through diatomaceous earth and / or activated clay and having a temperature of 35-45 ° C. To ensure the smoothness and luster of the surface of the plate, the rolling oil contained at least 95% base oil and 5% organic acids, alcohols or esters which are oily additives.

4) Intermediate annealing In a box-type annealing furnace, the obtained aluminum foil material was kept warm at 200 ° C. for 3 hours, then heated to 380 ° C. and kept warm for 6 hours. The metallographic structure was completely recrystallized, the hardening during cold rolling was removed, and the rolled texture was further converted into a recrystallized texture.

5) Aluminum Foil Rolling An annealed 0.56 mm thick aluminum foil material was roughly rolled, intermediately rolled, and finished rolled to produce a 0.042 mm thick single-sided glossy aluminum foil.

6) Division of aluminum foil The division stress was controlled to 30 MPa and the winding speed was controlled to 120 mm / min.

7) Final firing of aluminum foil The aluminum foil is heated to 130 ° C in a negative pressure circulation box furnace, kept warm for 30 hours, further heated to 180 ° C and kept warm for 25 hours, and further heated to 280 ° C to keep warm for 70 hours. Then, the ratio of the crystal grain structure and the aggregated structure of the aluminum foil was adjusted, and the aluminum foil was taken out of the furnace and air-cooled.

8) Performance measurement of aluminum foil The cubic texture of aluminum foil and the size of crystal grains were measured as follows, and the results are shown below.

First, the surface of the aluminum foil was electropolished, and then the surface of the aluminum foil was scanned in a scanning step of 2.5 μm with an EDAX model OIM2000 EBSD device equipped with a JSM6380 electron scanning electron microscope. Next, using the analytical software that came with the instrument, the cubic texture and grain size of the surface of the aluminum foil was statistic. As a result of the measurement, the aluminum foil produced in the example had a volume fraction of cubic texture of 11.9% and a crystal grain size of 15.3 μm.

The flexibility of the aluminum foil was measured as follows, and the results are shown below.

According to the method described in the national standard GB / T8942-2016 "Measurement of paper flexibility", the flexibility of the aluminum foil is measured with a tactile softness measuring device, and the maximum resistance of the measurement is defined as the flexibility of the aluminum foil. The unit was mN. The aluminum foil produced in the example had a flexibility of 364.1 mN.

The Eriksen value of the aluminum foil was measured as follows, and the results are shown below.

Using the GBS-60E digital display automatic cupping tester and 20 mm diameter punch, 27 mm diameter die attached to the equipment, according to the method described in National Standard GB / T4156-2007 "Metallic Materials-Ericsson Cupping Test for Thin Plates and Thin Strips". Then, the Elixin value of the aluminum foil was measured. During the measurement, the blank holder force was 10 KN, the punch speed was 10 mm / min, and the lubricant was petrolatum. The aluminum foil produced in the example had an Eriksen value of 7.5 mm.

The amount of residual oil on the surface of the aluminum foil was measured as follows, and the results are shown below.

According to the method described in Standard HJ637-2012 "Measurement of water quality, petroleum, animal and vegetable oils, infrared spectrophotometric method", the residual rolling oil on the surface of the aluminum foil sample is washed with an organic solvent, and the rolling oil in the organic solvent is carbon tetrachloride. Extracted with. After the oil was dissolved, the oil content in the solvent was measured using a NICOLET380 Fourier transform infrared spectrometer and converted into the residual oil amount per unit area. The aluminum foil produced in the example had a surface residual oil amount of 0.31 mg / m2.

<Example 5>
The soft pack aluminum foil was manufactured from a raw material having the following composition in% by mass.

Si: 0.10%, Fe: 1.62%, Cu: 0.04%, Mn: 0.0090%, Mg: 0.005%, Zn: 0.0016%, Cr: 0.009%, Ti : 0.0109%, V: 0.0030%, the balance consists of Al and unavoidable impurities.

The aluminum foil was manufactured as follows.

1) Homogenization Treatment of Ingots for Semi-Continuous Casting Both ends of a rectangular ingot produced by semi-continuous casting of the above raw materials were cut with a saw, and the amount cut with a saw was 30 mm. Milling was performed on the other four side surfaces (two large side surfaces and two small side surfaces), and the cutting amount on one side was 15 mm. Further, the ingot was homogenized in a heating furnace at 570 ° C. for 18 hours, and further kept warm at 450 ° C. for 5 hours.

2) Hot rolling The ingot was subjected to hot rough rolling and hot finish rolling using a 1 + 3 stage hot rolling unit equipped with a roll having a roll surface roughness of 0.63-1.25 μm. .. At the start of rolling, the ingot was rolled at a temperature of 450 ° C. and a plate material having a thickness of 5.5 mm at 320 ° C. with a deformation amount of 25-60% per pass, further wound up, and gradually cooled at room temperature. In hot rolling, in order to ensure good lubrication between the roll and the plate material, cooling action and surface quality of the plate material, an aqueous emulsion with a PH value of 7.5 and a temperature of 45-50 ° C. is used during rolling for lubrication. It was cooled.

3) Cold rolling Cold-rolled to a 1.0 mm aluminum foil material with a rolling reduction of 20-60% per pass. Of these, they were lubricated and cooled with rolling oil having a light transmittance of at least 95% filtered through diatomaceous earth and / or activated clay and having a temperature of 35-45 ° C. To ensure the smoothness and luster of the surface of the plate, the rolling oil contained at least 95% base oil and 5% organic acids, alcohols or esters which are oily additives.

4) Intermediate annealing In a box-type annealing furnace, the obtained aluminum foil material was kept warm at 180 ° C. for 5 hours, then heated to 370 ° C. and kept warm for 5 hours. The metallographic structure was completely recrystallized, the hardening during cold rolling was removed, and the rolled texture was further converted into a recrystallized texture.

5) Aluminum Foil Rolling An annealed 1.0 mm thick aluminum foil material was roughly rolled, intermediate rolled, and finished rolled to produce a single-sided glossy aluminum foil having a thickness of 0.038 mm.

6) Division of aluminum foil The division stress was controlled to 31 MPa and the winding speed was controlled to 100 mm / min.

7) Final annealing of aluminum foil The aluminum foil is heated to 110 ° C. in a negative pressure circulation box furnace and kept warm for 30 hours, then heated to 270 ° C. and kept warm for 50 hours, and the structure and aggregate structure of the crystal grains of the aluminum foil are obtained. The ratio was adjusted, and the mixture was taken out of the furnace and air-cooled.

8) Performance measurement of aluminum foil The cubic texture of aluminum foil and the size of crystal grains were measured as follows, and the results are shown below.

First, the surface of the aluminum foil was electropolished, and then the surface of the aluminum foil was scanned in a scanning step of 2.5 μm with an EDAX model OIM2000 EBSD device equipped with a JSM6380 electron scanning electron microscope. Next, using the analytical software that came with the instrument, the cubic texture and grain size of the surface of the aluminum foil was statistic. As a result of the measurement, the aluminum foil produced in the example had a volume fraction of a cubic texture of 8.1% and a crystal grain size of 12.7 μm.

The flexibility of the aluminum foil was measured as follows, and the results are shown below.

According to the method described in the national standard GB / T8942-2016 "Measurement of paper flexibility", the flexibility of the aluminum foil is measured with a tactile softness measuring device, and the maximum resistance of the measurement is defined as the flexibility of the aluminum foil. The unit was mN. The aluminum foil produced in the example had a flexibility of 395.2 mN.

The Eriksen value of the aluminum foil was measured as follows, and the results are shown below.

Using the GBS-60E digital display automatic cupping tester and 20 mm diameter punch, 27 mm diameter die attached to the equipment, according to the method described in National Standard GB / T4156-2007 "Metallic Materials-Ericsson Cupping Test for Thin Plates and Thin Strips". Then, the Elixin value of the aluminum foil was measured. During the measurement, the blank holder force was 10 KN, the punch speed was 10 mm / min, and the lubricant was petrolatum. The aluminum foil produced in the example had an Eriksen value of 7.1 mm.

The amount of residual oil on the surface of the aluminum foil was measured as follows, and the results are shown below.

According to the method described in Standard HJ637-2012 "Measurement of water quality, petroleum, animal and vegetable oils, infrared spectrophotometric method", the residual rolling oil on the surface of the aluminum foil sample is washed with an organic solvent, and the rolling oil in the organic solvent is carbon tetrachloride. Extracted with. After the oil was dissolved, the oil content in the solvent was measured using a NICOLET380 Fourier transform infrared spectrometer and converted into the residual oil amount per unit area. The aluminum foil produced in the example had a surface residual oil amount of 0.28 mg / m2.

<Example 6>
The soft pack aluminum foil was manufactured from a raw material having the following composition in% by mass.

Si: 0.051%, Fe: 1.35%, Cu: 0.031%, Mn: 0.021%, Mg: 0.005%, Zn: 0.051%, Cr: 0.0026%, Ti : 0.012%, V: 0.0027%, the balance consists of Al and unavoidable impurities.

The aluminum foil was manufactured as follows.

1) Homogenization Treatment of Ingots for Semi-Continuous Casting Both ends of a rectangular ingot produced by semi-continuous casting of the above raw materials were cut with a saw, and the amount cut with a saw was 30 mm. Milling was performed on the other four side surfaces (two large side surfaces and two small side surfaces), and the cutting amount on one side was 15 mm. Further, the ingot was homogenized in a heating furnace at 550 ° C. for 15 hours, and further kept warm at 500 ° C. for 3 hours.

2) Hot rolling The ingot was subjected to hot rough rolling and hot finish rolling using a 1 + 3 stage hot rolling unit equipped with a roll having a roll surface roughness of 0.63-1.25 μm. .. At the start of rolling, the ingot was rolled at a temperature of 500 ° C. and a plate material having a thickness of 3.8 mm at 300 ° C. with a deformation amount of 25-60% per pass, further wound up, and gradually cooled at room temperature. In hot rolling, in order to ensure good lubrication between the roll and the plate material, cooling action and surface quality of the plate material, an aqueous emulsion with a PH value of 7.8 and a temperature of 45-50 ° C. is used during rolling for lubrication. It was cooled.

3) Cold rolling Cold rolling was performed on an aluminum foil material of 1.5 mm at a rolling reduction of 20-60% per pass. Of these, they were lubricated and cooled with rolling oil having a light transmittance of at least 90% filtered through diatomaceous earth and / or activated clay and having a temperature of 35-45 ° C. To ensure the smoothness and luster of the surface of the plate, the rolling oil contained at least 95% base oil and 5% organic acids, alcohols or esters which are oily additives.

4) Intermediate annealing In a box-type annealing furnace, the obtained aluminum foil material was kept warm at 400 ° C. for 2 hours. The metallographic structure was completely recrystallized, the hardening during cold rolling was removed, and the rolled texture was further converted into a recrystallized texture.

5) Aluminum Foil Rolling An annealed 1.5 mm thick aluminum foil material was roughly rolled, intermediate rolled, and finished rolled to produce a single-sided glossy aluminum foil having a thickness of 0.045 mm.

6) Division of aluminum foil The division stress was controlled to 25 MPa and the winding speed was controlled to 140 mm / min.

7) Final annealing of aluminum foil The aluminum foil is heated to 100 ° C. in a negative pressure circulation box furnace and kept warm for 15 hours, then heated to 250 ° C. and kept warm for 60 hours, and the structure and aggregate structure of the crystal grains of the aluminum foil. The ratio was adjusted, and the mixture was taken out of the furnace and air-cooled.

8) Performance measurement of aluminum foil The cubic texture of aluminum foil and the size of crystal grains were measured as follows, and the results are shown below.

First, the surface of the aluminum foil was electropolished, and then the surface of the aluminum foil was scanned in a scanning step of 2.5 μm with an EDAX model OIM2000 EBSD device equipped with a JSM6380 electron scanning electron microscope. Next, using the analytical software that came with the instrument, the cubic texture and grain size of the surface of the aluminum foil was statistic. As a result of the measurement, the aluminum foil produced in the example had a volume fraction of the cubic texture of 7.0% and a crystal grain size of 12.3 μm.

The flexibility of the aluminum foil was measured as follows, and the results are shown below.

According to the method described in the national standard GB / T8942-2016 "Measurement of paper flexibility", the flexibility of the aluminum foil is measured with a tactile softness measuring device, and the maximum resistance of the measurement is defined as the flexibility of the aluminum foil. The unit was mN. The aluminum foil produced in the example had a flexibility of 410 mN.

The Eriksen value of the aluminum foil was measured as follows, and the results are shown below.

Using the GBS-60E digital display automatic cupping tester and 20 mm diameter punch, 27 mm diameter die attached to the equipment, according to the method described in National Standard GB / T4156-2007 "Metallic Materials-Ericsson Cupping Test for Thin Plates and Thin Strips". Then, the Ericssen value of the aluminum foil was measured. During the measurement, the blank holder force was 10 KN, the punch speed was 10 mm / min, and the lubricant was petrolatum. The aluminum foil produced in the example had an Eriksen value of 7.0 mm.

The amount of residual oil on the surface of the aluminum foil was measured as follows, and the results are shown below.

According to the method described in Standard HJ637-2012 "Measurement of water quality, petroleum, animal and vegetable oils, infrared spectrophotometric method", the residual rolling oil on the surface of the aluminum foil sample is washed with an organic solvent, and the rolling oil in the organic solvent is carbon tetrachloride. Extracted with. After the oil was dissolved, the oil content in the solvent was measured using a NICOLET380 Fourier transform infrared spectrometer and converted into the residual oil amount per unit area. The aluminum foil produced in the example had a surface residual oil amount of 0.29 mg / m2.

<Example 7>
The soft pack aluminum foil was manufactured from a raw material having the following composition in% by mass.

Si: 0.052%, Fe: 1.36%, Cu: 0.04%, Mn: 0.032%, Mg: 0.003%, Zn: 0.0022%, Cr: 0.0017%, Ti : 0.008%, V: 0.0034%, the balance consists of Al and unavoidable impurities.

The aluminum foil was manufactured as follows.

1) Homogenization Treatment of Ingots for Semi-Continuous Casting Both ends of a rectangular ingot produced by semi-continuous casting of the above raw materials were cut with a saw, and the amount cut with a saw was 30 mm. Milling was performed on the other four side surfaces (two large side surfaces and two small side surfaces), and the cutting amount on one side was 15 mm. Further, the ingot was homogenized in a heating furnace at 620 ° C. for 8 hours, further cooled to 500 ° C. together with the furnace, and prepared for hot rolling.

2) Hot rolling The ingot was subjected to hot rough rolling and hot finish rolling using a 1 + 3 stage hot rolling unit equipped with a roll having a roll surface roughness of 0.63-1.25 μm. .. At the start of rolling, the ingot was rolled at a temperature of 500 ° C. and a plate material having a thickness of 3.2 mm at 350 ° C. with a deformation amount of 25-60% per pass, further wound up, and gradually cooled at room temperature. In hot rolling, in order to ensure good lubrication between the roll and the plate material, cooling action and surface quality of the plate material, an aqueous emulsion with a PH value of 7.2 and a temperature of 45-50 ° C. is used during rolling for lubrication. It was cooled.

3) Cold rolling Cold rolling was performed on an aluminum foil material of 0.3 mm at a rolling reduction of 20-60% per pass. Of these, they were lubricated and cooled with rolling oil having a light transmittance of at least 96% filtered through diatomaceous earth and / or activated clay and having a temperature of 35-45 ° C. To ensure the smoothness and luster of the surface of the plate, the rolling oil contained at least 95% base oil and 5% organic acids, alcohols or esters which are oily additives.

4) Intermediate annealing In a box-type annealing furnace, the obtained aluminum foil material was kept warm at 150 ° C. for 3 hours, then heated to 330 ° C. and kept warm for 6 hours. The metallographic structure was completely recrystallized, the hardening during cold rolling was removed, and the rolled texture was further converted into a recrystallized texture.

5) Aluminum foil rolling The annealed 0.3 mm aluminum foil material was roughly rolled, intermediate rolled, and finished rolled to produce a single-sided glossy aluminum foil having a thickness of 0.035 mm.

6) Division of aluminum foil The division stress was controlled to 25 MPa and the winding speed was controlled to 90 mm / min.

7) Final annealing of aluminum foil The aluminum foil is heated to 70 ° C. in a negative pressure circulation box furnace and kept warm for 25 hours, then heated to 350 ° C. and kept warm for 65 hours, and the structure and aggregate structure of the crystal grains of the aluminum foil. The ratio was adjusted, and the mixture was taken out of the furnace and air-cooled.

8) Performance measurement of aluminum foil The cubic texture of aluminum foil and the size of crystal grains were measured as follows, and the results are shown below.

First, the surface of the aluminum foil was electropolished, and then the surface of the aluminum foil was scanned in a scanning step of 2.5 μm with an EDAX model OIM2000 EBSD device equipped with a JSM6380 electron scanning electron microscope. Next, using the analytical software that came with the instrument, the cubic texture and grain size of the surface of the aluminum foil was statistic. As a result of the measurement, the aluminum foil produced in the example had a volume fraction of cubic texture of 15.1% and a crystal grain size of 18.0 μm.

The flexibility of the aluminum foil was measured as follows, and the results are shown below.

According to the method described in the national standard GB / T8942-2016 "Measurement of paper flexibility", the flexibility of the aluminum foil is measured with a tactile softness measuring device, and the maximum resistance of the measurement is defined as the flexibility of the aluminum foil. The unit was mN. The aluminum foil produced in the example had a flexibility of 340 mN.

The Eriksen value of the aluminum foil was measured as follows, and the results are shown below.

Using the GBS-60E digital display automatic cupping tester and 20 mm diameter punch, 27 mm diameter die attached to the equipment, according to the method described in National Standard GB / T4156-2007 "Metallic Materials-Ericsson Cupping Test for Thin Plates and Thin Strips". Then, the Ericssen value of the aluminum foil was measured. During the measurement, the blank holder force was 10 KN, the punch speed was 10 mm / min, and the lubricant was petrolatum. The aluminum foil produced in the example had an Eriksen value of 6.5 mm.

The amount of residual oil on the surface of the aluminum foil was measured as follows, and the results are shown below.

According to the method described in Standard HJ637-2012 "Measurement of water quality, petroleum, animal and vegetable oils, infrared spectrophotometric method", the residual rolling oil on the surface of the aluminum foil sample is washed with an organic solvent, and the rolling oil in the organic solvent is carbon tetrachloride. Extracted with. After the oil was dissolved, the oil content in the solvent was measured using a NICOLET380 Fourier transform infrared spectrometer and converted into the residual oil amount per unit area. The aluminum foil produced in the example had a surface residual oil amount of 0.20 mg / m2.

<Example 8>
The soft pack aluminum foil was manufactured from a raw material having the following composition in% by mass.

Si: 0.12%, Fe: 1.66%, Cu: 0.002%, Mn: 0.006%, Mg: 0.003%, Zn: 0.0025%, Cr: 0.0037%, Ti : 0.008%, V: 0.0014%, the balance consists of Al and unavoidable impurities.

The aluminum foil was manufactured as follows.

1) Homogenization Treatment of Ingots for Semi-Continuous Casting Both ends of a rectangular ingot produced by semi-continuous casting of the above raw materials were cut with a saw, and the amount cut with a saw was 30 mm. Milling was performed on the other four side surfaces (two large side surfaces and two small side surfaces), and the cutting amount on one side was 15 mm. Further, the ingot was heated to 550 in a heating furnace and prepared for hot rolling.

2) Hot rolling The ingot was subjected to hot rough rolling and hot finish rolling using a 1 + 3 stage hot rolling unit equipped with a roll having a roll surface roughness of 0.63-1.25 μm. .. At the start of rolling, the ingot was rolled at a temperature of 550 ° C. and a plate material having a thickness of 6.2 mm at 340 ° C. with a deformation amount of 25-60% per pass, further wound up, and gradually cooled at room temperature. In hot rolling, in order to ensure good lubrication between the roll and the plate material, cooling action and surface quality of the plate material, an aqueous emulsion with a PH value of 7.2 and a temperature of 45-50 ° C. is used during rolling for lubrication. It was cooled.

3) Cold rolling Cold-rolled to a 1.6 mm aluminum foil material with a rolling reduction of 20-60% per pass. Of these, they were lubricated and cooled with rolling oil having a light transmittance of at least 97% filtered through diatomaceous earth and / or activated clay and having a temperature of 35-45 ° C. To ensure the smoothness and luster of the surface of the plate, the rolling oil contained at least 95% base oil and 5% organic acids, alcohols or esters which are oily additives.

4) Intermediate annealing In a box-type annealing furnace, the obtained aluminum foil material was kept warm at 210 ° C. for 4 hours, then heated to 400 ° C. and kept warm for 6 hours. The metallographic structure was completely recrystallized, the hardening during cold rolling was removed, and the rolled texture was further converted into a recrystallized texture.

5) Aluminum foil rolling The annealed 1.6 mm thick aluminum foil material was roughly rolled, intermediate rolled, and finished rolled to produce a single-sided glossy aluminum foil having a thickness of 0.048 mm.

6) Division of aluminum foil The division stress was controlled to be 27 MPa and the winding speed was controlled to 90 mm / min.

7) Final annealing of aluminum foil The aluminum foil is heated to 90 ° C. in a negative pressure circulation box furnace and kept warm for 20 hours, then heated to 240 ° C. and kept warm for 80 hours, and the structure and aggregate structure of the crystal grains of the aluminum foil are obtained. The ratio was adjusted, and the mixture was taken out of the furnace and air-cooled.

8) Performance measurement of aluminum foil The cubic texture of aluminum foil and the size of crystal grains were measured as follows, and the results are shown below.

First, the surface of the aluminum foil was electropolished, and then the surface of the aluminum foil was scanned in a scanning step of 2.5 μm with an EDAX model OIM2000 EBSD device equipped with a JSM6380 electron scanning electron microscope. Next, using the analytical software that came with the instrument, the cubic texture and grain size of the surface of the aluminum foil was statistic. As a result of the measurement, the aluminum foil produced in the example had a volume fraction of the cubic texture of 6.2% and a crystal grain size of 10.4 μm.

The flexibility of the aluminum foil was measured as follows, and the results are shown below.

According to the method described in the national standard GB / T8942-2016 "Measurement of paper flexibility", the flexibility of the aluminum foil is measured with a tactile softness measuring device, and the maximum resistance of the measurement is defined as the flexibility of the aluminum foil. The unit was mN. The aluminum foil produced in the example had a flexibility of 425 mN.

The Eriksen value of the aluminum foil was measured as follows, and the results are shown below.

Using the GBS-60E digital display automatic cupping tester and 20 mm diameter punch, 27 mm diameter die attached to the equipment, according to the method described in National Standard GB / T4156-2007 "Metallic Materials-Ericsson Cupping Test for Thin Plates and Thin Strips". Then, the Elixin value of the aluminum foil was measured. During the measurement, the blank holder force was 10 KN, the punch speed was 10 mm / min, and the lubricant was petrolatum. The aluminum foil produced in the example had an Eriksen value of 6.3 mm.

The amount of residual oil on the surface of the aluminum foil was measured as follows, and the results are shown below.

According to the method described in Standard HJ637-2012 "Measurement of water quality, petroleum, animal and vegetable oils, infrared spectrophotometric method", the residual rolling oil on the surface of the aluminum foil sample is washed with an organic solvent, and the rolling oil in the organic solvent is carbon tetrachloride. Extracted with. After the oil was dissolved, the oil content in the solvent was measured using a NICOLET380 Fourier transform infrared spectrometer and converted into the residual oil amount per unit area. The aluminum foil produced in the example had a surface residual oil amount of 0.22 mg / m2.

<Example 9>
The soft pack aluminum foil was manufactured from a raw material having the following composition in% by mass.

Si: 0.12%, Fe: 1.66%, Cu: 0.002%, Mn: 0.006%, Mg: 0.003%, Zn: 0.0025%, Cr: 0.0037%, Ti : 0.008%, V: 0.0014%, the balance consists of Al and unavoidable impurities.

The aluminum foil was manufactured as follows.

1) Homogenization Treatment of Ingots for Semi-Continuous Casting Both ends of a rectangular ingot produced by semi-continuous casting of the above raw materials were cut with a saw, and the amount cut with a saw was 30 mm. Milling was performed on the other four side surfaces (two large side surfaces and two small side surfaces), and the cutting amount on one side was 15 mm. Further, the ingot was heated to 550 in a heating furnace and prepared for hot rolling.

2) Hot rolling The ingot was subjected to hot rough rolling and hot finish rolling using a 1 + 3 stage hot rolling unit equipped with a roll having a roll surface roughness of 0.63-1.25 μm. .. At the start of rolling, the ingot was rolled at a temperature of 550 ° C. and a plate material having a thickness of 6.5 mm at 360 ° C. with a deformation amount of 25-60% per pass, further wound up, and gradually cooled at room temperature. In hot rolling, in order to ensure good lubrication between the roll and the plate material, cooling action and surface quality of the plate material, an aqueous emulsion with a PH value of 7.2 and a temperature of 45-50 ° C. is used during rolling for lubrication. It was cooled.

3) Cold rolling Cold rolling was performed on an aluminum foil material of 1.3 mm at a rolling reduction of 20-60% per pass. Of these, they were lubricated and cooled with rolling oil having a light transmittance of at least 94% filtered through diatomaceous earth and / or activated clay and having a temperature of 35-45 ° C. To ensure the smoothness and luster of the surface of the plate, the rolling oil contained at least 95% base oil and 5% organic acids, alcohols or esters which are oily additives.

4) Intermediate annealing In a box-type annealing furnace, the obtained aluminum foil material was kept warm at 390 ° C. for 6 hours. The metallographic structure was completely recrystallized, the hardening during cold rolling was removed, and the rolled texture was further converted into a recrystallized texture.

5) Aluminum Foil Rolling An annealed 1.3 mm thick aluminum foil material was roughly rolled, intermediate rolled, and finished rolled to produce a 0.03 mm thick single-sided glossy aluminum foil.

6) Division of aluminum foil The division stress was controlled to be 27 MPa and the winding speed was controlled to 140 mm / min.

7) Final annealing of aluminum foil The aluminum foil is heated to 75 ° C. in a negative pressure circulation box furnace and kept warm for 15 hours, then heated to 390 ° C. and kept warm for 60 hours, and the structure and aggregate structure of the crystal grains of the aluminum foil. The ratio was adjusted, and the mixture was taken out of the furnace and air-cooled.

8) Performance measurement of aluminum foil The cubic texture of aluminum foil and the size of crystal grains were measured as follows, and the results are shown below.

First, the surface of the aluminum foil was electropolished, and then the surface of the aluminum foil was scanned in a scanning step of 2.5 μm with an EDAX model OIM2000 EBSD device equipped with a JSM6380 electron scanning electron microscope. Next, using the analytical software that came with the instrument, the cubic texture and grain size of the surface of the aluminum foil was statistic. As a result of the measurement, the aluminum foil produced in the example had a volume fraction of 16.0% and a crystal grain size of 20.0 μm.

The flexibility of the aluminum foil was measured as follows, and the results are shown below.

According to the method described in the national standard GB / T8942-2016 "Measurement of paper flexibility", the flexibility of the aluminum foil is measured with a tactile softness measuring device, and the maximum resistance of the measurement is defined as the flexibility of the aluminum foil. The unit was mN. The aluminum foil produced in the example had a flexibility of 335 mN.

The Eriksen value of the aluminum foil was measured as follows, and the results are shown below.

Using the GBS-60E digital display automatic cupping tester and 20 mm diameter punch, 27 mm diameter die attached to the equipment, according to the method described in National Standard GB / T4156-2007 "Metallic Materials-Ericsson Cupping Test for Thin Plates and Thin Strips". Then, the Elixin value of the aluminum foil was measured. During the measurement, the blank holder force was 10 KN, the punch speed was 10 mm / min, and the lubricant was petrolatum. The aluminum foil produced in the example had an Eriksen value of 6.1 mm.

The amount of residual oil on the surface of the aluminum foil was measured as follows, and the results are shown below.

According to the method described in Standard HJ637-2012 "Measurement of water quality, petroleum, animal and vegetable oils, infrared spectrophotometric method", the residual rolling oil on the surface of the aluminum foil sample is washed with an organic solvent, and the rolling oil in the organic solvent is carbon tetrachloride. Extracted with. After the oil was dissolved, the oil content in the solvent was measured using a NICOLET380 Fourier transform infrared spectrometer and converted into the residual oil amount per unit area. The aluminum foil produced in the example had a surface residual oil amount of 0.32 mg / m2.

<Example 10>
The soft pack aluminum foil was manufactured from a raw material having the following composition in% by mass.

Si: 0.1%, Fe: 1.62%, Cu: 0.04%, Mn: 0.009%, Mg: 0.005%, Zn: 0.0016%, Cr: 0.009%, Ti : 0.01%, V: 0.003%, the balance consists of Al and unavoidable impurities.

The aluminum foil was manufactured as follows.

1) Homogenization Treatment of Ingots for Semi-Continuous Casting Both ends of a rectangular ingot produced by semi-continuous casting of the above raw materials were cut with a saw, and the amount cut with a saw was 30 mm. Milling was performed on the other four side surfaces (two large side surfaces and two small side surfaces), and the cutting amount on one side was 15 mm. Further, the ingot was homogenized in a heating furnace at 610 ° C. for 15 hours, further cooled to 510 ° C. together with the furnace, and kept warm for 3 hours.

2) Hot rolling The ingot was subjected to hot rough rolling and hot finish rolling using a 1 + 3 stage hot rolling unit equipped with a roll having a roll surface roughness of 0.63-1.25 μm. .. At the start of rolling, the ingot was rolled to a plate material having a thickness of 6.3 mm at 330 ° C. with a deformation amount of 25-60% at 510 ° C., further wound up, and gradually cooled at room temperature. In hot rolling, in order to ensure good lubrication between the roll and the plate material, cooling action and surface quality of the plate material, an aqueous emulsion with a PH value of 7.2 and a temperature of 45-50 ° C. is used during rolling for lubrication. It was cooled.

3) Cold rolling Cold rolling was performed on an aluminum foil material of 0.8 mm at a rolling reduction of 20-60% per pass. Of these, they were lubricated and cooled with rolling oil having a light transmittance of at least 96% filtered through diatomaceous earth and / or activated clay and having a temperature of 35-45 ° C. To ensure the smoothness and luster of the surface of the plate, the rolling oil contained at least 95% base oil and 5% organic acids, alcohols or esters which are oily additives.

4) Intermediate annealing In a box-type annealing furnace, the obtained aluminum foil material was kept warm at 130 ° C. for 4 hours, then heated to 380 ° C. and kept warm for 3 hours. The metallographic structure was completely recrystallized, the hardening during cold rolling was removed, and the rolled texture was further converted into a recrystallized texture.

5) Aluminum Foil Rolling An annealed 0.8 mm thick aluminum foil material was roughly rolled, intermediate rolled, and finished rolled to produce a 0.037 mm thick single-sided glossy aluminum foil.

6) Division of aluminum foil The division stress was controlled to 32 MPa and the winding speed was controlled to 105 mm / min.

7) Final annealing of aluminum foil The aluminum foil is heated to 90 ° C. in a negative pressure circulation box furnace and kept warm for 10 hours, then heated to 270 ° C. and kept warm for 90 hours, and the structure and aggregate structure of the crystal grains of the aluminum foil are obtained. The ratio was adjusted, and the mixture was taken out of the furnace and air-cooled.

8) Performance measurement of aluminum foil The cubic texture of aluminum foil and the size of crystal grains were measured as follows, and the results are shown below.

First, the surface of the aluminum foil was electropolished, and then the surface of the aluminum foil was scanned in a scanning step of 2.5 μm with an EDAX model OIM2000 EBSD device equipped with a JSM6380 electron scanning electron microscope. Next, using the analytical software that came with the instrument, the cubic texture and grain size of the surface of the aluminum foil was statistic. As a result of the measurement, the aluminum foil produced in the example had a volume fraction of the cubic texture of 7.5% and a crystal grain size of 12.4 μm.

The flexibility of the aluminum foil was measured as follows, and the results are shown below.

According to the method described in the national standard GB / T8942-2016 "Measurement of paper flexibility", the flexibility of the aluminum foil is measured with a tactile softness measuring device, and the maximum resistance of the measurement is defined as the flexibility of the aluminum foil. The unit was mN. The aluminum foil produced in the example had a flexibility of 400 mN.

The Eriksen value of the aluminum foil was measured as follows, and the results are shown below.

Using the GBS-60E digital display automatic cupping tester and 20 mm diameter punch, 27 mm diameter die attached to the equipment, according to the method described in National Standard GB / T4156-2007 "Metallic Materials-Ericsson Cupping Test for Thin Plates and Thin Strips". Then, the Elixin value of the aluminum foil was measured. During the measurement, the blank holder force was 10 KN, the punch speed was 10 mm / min, and the lubricant was petrolatum. The aluminum foil produced in the example had an Eriksen value of 6.9 mm.

The amount of residual oil on the surface of the aluminum foil was measured as follows, and the results are shown below.

According to the method described in Standard HJ637-2012 "Measurement of water quality, petroleum, animal and vegetable oils, infrared spectrophotometric method", the residual rolling oil on the surface of the aluminum foil sample is washed with an organic solvent, and the rolling oil in the organic solvent is carbon tetrachloride. Extracted with. After the oil was dissolved, the oil content in the solvent was measured using a NICOLET380 Fourier transform infrared spectrometer and converted into the residual oil amount per unit area. The aluminum foil produced in the example had a surface residual oil amount of 0.39 mg / m2.

<Example 11>
The soft pack aluminum foil was manufactured from a raw material having the following composition in% by mass.

Si: 0.052%, Fe: 1.36%, Cu: 0.014%, Mn: 0.017%, Mg: 0.005%, Zn: 0.012%, Cr: 0.0007%, Ti : 0.01%, V: 0.0014%, the balance consists of Al and unavoidable impurities.

The aluminum foil was manufactured as follows.

1) Homogenization of ingots for semi-continuous casting The amount of the rectangular ingot manufactured by semi-continuous casting of the above raw materials is cut at both ends and the other four sides with a saw, and the amount cut with a saw at the ends and sides. They were homogenized at 30 mm and 15 mm, respectively, in a heating furnace at 590 ° C. for 15 hours, and further kept warm at 500 ° C. for 2 hours.

2) Hot rolling Using a 1 + 1-stage hot rolling unit equipped with a roll having a roll surface roughness of 0.63-1.25 μm under lubrication of an aqueous emulsion having a pH value of 7.5 and a temperature of 45-50 ° C. Then, the ingot at 500 ° C. was rolled. When rolled to a thickness of 4.7 mm with a deformation amount of 25-60% per pass, it was wound at 280 ° C. and cooled at room temperature.

3) Cold rolling Cold rolling was performed on an aluminum foil material of 0.55 mm at a rolling reduction rate of 20-60% per pass. Of these, they were lubricated and cooled with rolling oil having a light transmittance of at least 95% filtered through diatomaceous earth and / or activated clay and having a temperature of 40-45 ° C. The rolling oil contained at least 95% base oil and 5% organic acids, alcohols or esters which are oily additives.

4) Intermediate annealing In a box-type annealing furnace, the obtained aluminum foil material was kept warm at 340 ° C. for 7 hours.

5) Aluminum foil rolling The annealed 0.55 mm aluminum foil material was roughly rolled, intermediate rolled, and finished rolled to produce a 0.04 mm thick single-sided glossy aluminum foil.

6) Division of aluminum foil The division stress was controlled to be 26 MPa and the winding speed was controlled to 140 mm / min.

7) Final annealing of aluminum foil The aluminum foil was annealed in a negative pressure circulation box furnace, kept at 90 ° C. for 20 hours, further heated to 250 ° C., kept warm for 90 hours, taken out of the furnace, and air-cooled.

8) Performance measurement of aluminum foil The cubic texture of aluminum foil and the size of crystal grains were measured as follows, and the results are shown below.

First, the surface of the aluminum foil was electropolished, and then the surface of the aluminum foil was scanned in a scanning step of 2.5 μm with an EDAX model OIM2000 EBSD device equipped with a JSM6380 electron scanning electron microscope. Next, using the analytical software that came with the instrument, the cubic texture and grain size of the surface of the aluminum foil was statistic. As a result of the measurement, the aluminum foil produced in the example had a volume fraction of cubic texture of 10.8% and a crystal grain size of 14.6 μm.

The flexibility of the aluminum foil was measured as follows, and the results are shown below.

According to the method described in the national standard GB / T8942-2016 "Measurement of paper flexibility", the flexibility of the aluminum foil is measured with a tactile softness measuring device, and the maximum resistance of the measurement is defined as the flexibility of the aluminum foil. The unit was mN. The aluminum foil produced in the example had a flexibility of 368.9 mN.

The Eriksen value of the aluminum foil was measured as follows, and the results are shown below.

Using the GBS-60E digital display automatic cupping tester and 20 mm diameter punch, 27 mm diameter die attached to the equipment, according to the method described in National Standard GB / T4156-2007 "Metallic Materials-Ericsson Cupping Test for Thin Plates and Thin Strips". Then, the Elixin value of the aluminum foil was measured. During the measurement, the blank holder force was 10 KN, the punch speed was 10 mm / min, and the lubricant was petrolatum. The aluminum foil produced in the example had an Eriksen value of 7.3 mm.

The amount of residual oil on the surface of the aluminum foil was measured as follows, and the results are shown below.

According to the method described in Standard HJ637-2012 "Measurement of water quality, petroleum, animal and vegetable oils, infrared spectrophotometric method", the residual rolling oil on the surface of the aluminum foil sample is washed with an organic solvent, and the rolling oil in the organic solvent is carbon tetrachloride. Extracted with. After the oil was dissolved, the oil content in the solvent was measured using a NICOLET380 Fourier transform infrared spectrometer and converted into the residual oil amount per unit area. The aluminum foil produced in this example had a surface residual oil amount of 0.29 mg / m2. The product performances of each of the examples and comparative examples of the present invention are shown in Table 1 below.

The above examples are used only for explaining the technical embodiments of the present invention, and are not limited thereto. Although the present invention has been described in detail with reference to the above examples, modifications or equivalent replacements that are still capable of modifying or equivalent to the embodiments of the invention and do not deviate from the gist and scope of the invention. It is readily apparent to those skilled in the art that is included in the claims of the present invention.

Claims (14)

By mass%, Fe: 0.7-2.0 wt% (preferably 0.7-1.7 wt%, more preferably 1.0-1.5 wt%), Si: 0.02-0.9 wt% (preferably 0.7-0.9 wt%). Preferably 0.05-0.1 wt%, more preferably 0.05-0.08 wt%), Cu: 0.5 wt% or less (preferably 0.001-0.5 wt%, preferably 0.05 wt% or less) , More preferably 0.0015-0.05 wt%), Mg: 0.1 wt% or less (preferably 0.001-0.1 wt%, preferably 0.05 wt% or less, more preferably 0.001-0. 008 wt%), Mn: 0.7 wt% or less (preferably 0.005-0.7 wt%, preferably 0.05 wt% or less, more preferably 0.007-0.04 wt%), Zn: 0.05 wt% Below (preferably 0.001-0.03 wt%, more preferably 0.01-0.02 wt%), Cr: 0.05 wt% or less (preferably 0.0005-0.05 wt%, preferably 0.005 wt%) % Or less, more preferably 0.0007-0.002 wt%), Ti: 0.1 wt% or less (preferably 0.001-0.1 wt%, preferably 0.02 wt% or less, more preferably 0.007- 0.02 wt%), V: 0.05 wt% or less (preferably 0.0005-0.05 wt%, preferably 0.02 wt% or less, preferably 0.01 wt% or less, preferably 0.0005-0.01 wt) %, preferably 0.0005-0.0034 wt%, more preferably 0.009-0.0015 wt%), the balance consisting of Al and unavoidable impurities, and the body integration ratio of the cubic aggregate is 5-20% (preferably 0.0015 wt%). 8-15%, more preferably 9-14%) and an average surface crystal grain size of 5-35 μm (preferably 10-20 μm, more preferably 12-18 μm). .. The flexibility of the aluminum foil is 450 mN or less (preferably 330-450 mN, more preferably 340-420 mN, more preferably 350-395 mN), and the Eriksen value of the aluminum foil is 5.0 mm or more (preferably 5.0). The aluminum foil according to claim 1, which is -10.0 mm, more preferably 6.0-9.0 mm, more preferably 7.0-8.0 mm). Intermediate annealing step: An aluminum foil material (preferably 0.1-2.0 mm thick, more preferably 0.3-1.0 mm thick) is intermediately annealed to obtain an annealed aluminum foil material.
Rolling process: The annealed aluminum foil material is rolled to obtain an aluminum foil (also called a semi-finished aluminum foil), and the final annealing step: The semi-finished aluminum foil is finally annealed to obtain an aluminum foil (also called a finished aluminum foil). With the process of getting (called),
The intermediate annealing step includes at least an annealing step A1, the annealing temperature of the annealing step A1 (referred to as annealing temperature A1) is 300-395 ° C (preferably 340-380 ° C), and the final annealing step is at least an annealing step. The annealing step B2 after the annealing step B1 is included, and the annealing temperature (referred to as the annealing temperature B1) of the annealing step B1 is 70-150 ° C (preferably 90-140 ° C), and the annealing step B2. A method for producing an aluminum foil, characterized in that the annealing temperature (referred to as annealing temperature B2) is 220-350 ° C (preferably 250-300 ° C or 250-280 ° C). The annealing temperature A1 is 50-150 ° C higher (preferably 70-100 ° C higher) than the annealing temperature B2, and / or the annealing temperature B2 is 80-200 ° C higher (preferably 105) than the annealing temperature B1. -185 ° C.) The production method according to claim 3. The intermediate annealing step includes at least keeping the aluminum foil material at a temperature of 300-400 ° C. (preferably 340-380 ° C.) (annealing temperature A1), or at least the aluminum foil material at 150-180 ° C. The production method according to claim 3, further comprising a step of keeping the temperature at 300-400 ° C (preferably 340-380 ° C) (annealing temperature A1). The rolling step includes a step of rough rolling, intermediate rolling, and finish rolling of the annealed aluminum foil material, and in the rough rolling, the annealed aluminum foil material is preferably 0.2-0.5 mm thick (preferably). Is rolled into a roll material having a thickness of 0.1-0.3 mm), and in the intermediate rolling, the roll material has a thickness of 0.05-0.2 mm (preferably 0.07-0.1 mm). Rolled into an aluminum foil, and in the finish rolling, the aluminum foil is 0.025-0.06 mm thick (preferably 0.03-0.05 mm thick, more preferably 0.035-0.045 mm thick). The manufacturing method according to claim 3, wherein the product is rolled into an aluminum foil (that is, the semi-finished aluminum foil). In the final annealing step, the temperature is kept at a temperature of at least 70-150 ° C (preferably 90-140 ° C) (annealing temperature B1), and then a temperature of 220-350 ° C (preferably 250-280 ° C) (annealing temperature B2). ), Or at least 70-150 ° C (preferably 90-140 ° C) (annealing temperature B1), then 220-350 ° C (preferably 250-280 ° C). The manufacturing method according to claim 3, further comprising a step of keeping the temperature at (annealing temperature B2) and then air-cooling. The production according to claim 3, further comprising a splitting step prior to the final annealing step, in which the splitting stress is 25-35 MPa and / or the take-up speed is 50-150 mm / min. Method. The manufacturing method according to claim 3, further comprising a step of subjecting an ingot of an aluminum alloy to a homogenization treatment, a hot rolling treatment and a cold rolling treatment to obtain an aluminum foil material. The homogenization treatment includes at least a step of keeping the ingot of the aluminum alloy at a temperature of 550-620 ° C. (preferably 570-610 ° C.), and preferably at least the ingot of the aluminum alloy at 550-620 ° C. (preferably). The production method according to claim 9, further comprising a step of keeping the temperature at 570-610 ° C.) and then further keeping the temperature at 400-520 ° C. (preferably 450-510 ° C.). The production according to claim 9, wherein the hot rolling process includes a step of rolling at least the homogenized aluminum alloy ingot into a 3-7 mm plate material (called a hot rolled plate material) at a temperature of at least 450 ° C. Method. In the cold rolling process, at least the hot-rolled plate material is rolled into the aluminum foil material having a thickness of 0.1-2.0 mm (preferably 0.3-1.0 mm) at a temperature of 80 ° C. or lower. The manufacturing method according to claim 9, which comprises a step. A packaging material for a soft pack lithium ion battery (particularly for a soft pack lithium ion battery), which comprises the aluminum foil according to claim 1 or the aluminum foil produced by the production method according to claim 3 and at least one polymer layer. Aluminum laminated film). A soft-packed lithium-ion battery comprising a positive electrode, a negative electrode, an electrolyte, a separator, and a packaging material for the soft-packed lithium-ion battery according to claim 13.