Classifications

• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
  • C23C18/54—Contact plating, i.e. electroless electrochemical plating
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C38/00—Ferrous alloys, e.g. steel alloys
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C38/00—Ferrous alloys, e.g. steel alloys
  • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C38/00—Ferrous alloys, e.g. steel alloys
  • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
  • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/64—Carriers or collectors
  • H01M4/66—Selection of materials
  • H01M4/661—Metal or alloys, e.g. alloy coatings
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
  • C23F1/00—Etching metallic material by chemical means
  • C23F1/10—Etching compositions
  • C23F1/14—Aqueous compositions
  • C23F1/16—Acidic compositions
  • C23F1/28—Acidic compositions for etching iron group metals
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K3/00—Apparatus or processes for manufacturing printed circuits
  • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
  • H05K3/382—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal
  • H05K3/383—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal by microetching

Definitions

• the present invention relates to an aqueous composition used for surface treatment of stainless steel, a method for roughening the surface of stainless steel using the aqueous composition, and the like.
• stainless steel has been considered for expansion into various fields in recent years due to its excellent durability and weather resistance.
• stainless steel is being increasingly used in housings for electronic parts, battery current collector foils, and automobile parts.
• the surface of the stainless steel is roughened for the purpose of adhering a dielectric substance or an organic substance.
• the surface of the stainless steel is roughened for the purpose of promoting heat dissipation.
• the roughening level is not always sufficient, and the treatment time and cost are increased because a complicated process is required. Therefore, a method has been desired that enables a sufficient roughening treatment to be efficiently applied to the surface of stainless steel in a simple process.
• the quality of the roughened stainless steel may be a problem.
• the problem that can occur has become clear.
• the present inventors can efficiently roughen the surface of stainless steel with sufficient and few steps by using an aqueous composition having a specific composition. At the same time, they have found that it is possible to realize a stainless steel of good quality in which extremely thin regions and pinholes are prevented from occurring, and have completed the present invention.
• the present invention is as follows.
• Hydrogen peroxide is contained in an amount of 0.1 to 10% by mass based on the total amount of the aqueous composition.
• Halide ion is contained in an amount of 1 to 30% by mass based on the total amount of the aqueous composition.
• the aqueous composition according to the above [1], wherein the compound that supplies the halide ion contains at least one selected from the group consisting of hydrochloric acid, sodium chloride, and copper chloride.
• the arithmetic mean roughness (Ra) of the surface of the roughened stainless steel specified by JIS B 0601-2001 is 0.04 ⁇ m higher than the arithmetic mean roughness (Ra) of the flat surface of the untreated stainless steel.
• the stainless steel is defined by JIS G4305 standard.
• Chromium-nickel stainless steel containing SUS304, SUS316, SUS3211, SUS347, and SUS329J1; Ferritic stainless steel (chrome stainless steel) containing SUS405, SUS430, SUS434, SUS444, SUS447, SUSXM27; and Precipitation hardening system (chromium / nickel stainless steel) containing SUS630, SUS631, and SUH660; The method for roughening stainless steel according to any one of the above [5] to [14], which is at least one of the above.
• a method for producing roughened stainless steel which comprises a roughening treatment step for roughening the surface of stainless steel using the aqueous composition according to any one of [1] to [4] above.
• the stainless steel is defined by JIS G4305 standard.
• Chromium-nickel stainless steel containing SUS304, SUS316, SUS3211, SUS347, and SUS329J1; Ferritic stainless steel (chrome stainless steel) containing SUS405, SUS430, SUS434, SUS444, SUS447, SUSXM27; and Precipitation hardening system (chromium / nickel stainless steel) containing SUS630, SUS631, and SUH660; The method for producing roughened stainless steel according to the above [16], which is at least one of the above. [18] The method for producing roughened stainless steel according to the above [16] or [17], wherein the stainless steel is a stainless steel foil.
• the surface of stainless steel can be sufficiently roughened by an efficient method with a small number of steps, and the quality is good in which extremely thin regions and pinholes are prevented from occurring. It is possible to stably obtain roughened stainless steel.
• the aqueous composition of the present invention is suitably used for a treatment for roughening a metal surface, that is, a treatment for roughening a metal surface and expanding irregularities.
• Preferred objects to be roughened with the aqueous composition of the present invention include various stainless steels whose details will be described later.
• the aqueous composition of the present invention contains 0.1 to 10% by mass of hydrogen hydrogen, 1 to 30% by mass of a halide ion, and 0 to 3% by mass of copper ion based on the total amount of the aqueous composition. include.
• the aqueous composition may include water and the like, in particular ion-exchanged water or ultrapure water.
• each component of the aqueous composition will be described.
• Hydrogen peroxide contained in the aqueous composition is usually mixed with other components as an aqueous solution having an appropriate concentration.
• concentration of hydrogen peroxide in the aqueous hydrogen peroxide solution used for producing the aqueous composition is not particularly limited, and may be, for example, 10 to 90%, and 35% to 60% according to industrial standards. Is preferable.
• hydrogen peroxide may contain a stabilizer up to about 0.01% by mass, and examples of an acceptable stabilizer include sulfuric acid and phosphoric acid.
• the production process and acquisition route of hydrogen peroxide are not limited, and for example, those produced by the anthraquinone method and the like are used.
• the concentration of hydrogen peroxide in the aqueous composition is 0.1 to 10% by mass, preferably 0.12 to 7% by mass, more preferably, based on the total amount (total mass) of the aqueous composition. Is 0.15 to 5% by mass, or 0.1 to 3% by mass, and may be 0.1 to 2% by mass (less than). Further, the lower limit of the concentration of hydrogen peroxide in the aqueous composition is, for example, 0.001% by mass, 0.01% by mass, 0.05% by mass, 0 based on the total amount (total mass) of the aqueous composition.
• .15% by mass, 0.2% by mass, 0.3% by mass, 0.5% by mass, 1.0% by mass, 1.5% by mass, 2.0% by mass may be used in an aqueous composition.
• the upper limit of the concentration of hydrogen peroxide contained is, for example, 15% by mass, 12% by mass, 10% by mass, 7% by mass, 6% by mass, and 5% by mass based on the total amount (total mass) of the aqueous composition. 4, 4% by mass, 3.5% by mass, 3% by mass, 2.5% by mass, 2% by mass, 1.5% by mass and the like.
• the range of the concentration of hydrogen peroxide is a range in which the above-mentioned lower limit value and upper limit value are appropriately combined, for example, 0.001 to 15% by mass, 0.01 to 15% by mass, 0.05 to 12% by mass, and 0. .05-7% by mass, 0.1-7% by mass, 0.1-5% by mass, 0.1-3% by mass, 0.1-2% by mass, 0.2-10% by mass, 0.2 It can be appropriately selected from ⁇ 7% by mass, 0.2 to 6% by mass, 0.2 to 5% by mass, 0.3 to 3% by mass and the like.
• the concentration of hydrogen peroxide in the above range By setting the concentration of hydrogen peroxide in the above range, the action and effect of the present invention tend to be more preferably achieved, and copper ions, halide ions and the like, which will be described later, coexist in the aqueous composition. However, the possibility of heat generation or foaming due to the decomposition of hydrogen peroxide is suppressed, and work safety is ensured.
• the type of the halide ion contained in the aqueous composition is not particularly limited, and may be, for example, a fluoride ion, a chloride ion, a bromide ion, or an iodide ion, but the chloride ion is easy to handle and economical. More preferable from the viewpoint of sex.
• the halogen compound that gives the halide ion is not particularly limited, and is, for example, a halide of an alkali metal such as sodium halide and potassium halide, a halide of an alkaline earth metal such as calcium halide, and a halogen.
• Examples include ammonium oxide, copper halide, and hydrogen halide.
• a halide of an alkali metal or a hydrogen halide is preferable, and hydrochloric acid or sodium chloride is more preferable, from the viewpoint of more effectively and surely exerting the action and effect of the present invention.
• the halogen compound is used alone or in combination of two or more.
• the halogen compound may overlap with the following copper compound.
• the copper halide also corresponds to the following copper compound as a copper ion source.
• the halogenated copper copper chloride is preferable.
• Halogen compounds (halide ions) cause pitting corrosion on the passivation film in the roughening treatment of the stainless steel surface.
• the concentration of halide ions in the aqueous composition is 1 to 30% by mass, preferably 2.0 to 25% by mass, more preferably 2.0 to 25% by mass, based on the total amount (total mass) of the aqueous composition. It is 4.0 to 22% by mass or 3.0 to 20% by mass, and particularly preferably 5.0 to 15% by mass, 8 to 15% by mass, or 10 to 15% by mass.
• the range of the concentration of halide ions in the aqueous composition is 0.01% by mass, 0.1% by mass, 0.5% by mass, and 1.0% by mass based on the total amount (total mass) of the aqueous composition.
• the range of the halide ion concentration is a range in which the above-mentioned lower limit value and upper limit value are appropriately combined, for example, 0.1 to 24% by mass, 1.0 to 24% by mass, 0.1 to 22% by mass, 1.
• the concentration of the halide ion in the above range, the action and effect of the present invention tend to be more preferably achieved. More specifically, in the aqueous composition in which the concentration of the halide ion is within the above range, the roughened shape can be developed while preventing the progress of the pitting reaction of the stainless steel, and the hydrogen peroxide can be expressed. Safety can be ensured by preventing decomposition reactions.
• the concentration of copper ions in the aqueous composition is 0 to 3% by mass based on the total amount (total mass) of the aqueous composition. That is, the aqueous composition in the present invention does not contain copper ions, or the content of copper ions is 3% by mass or less based on the total amount (total mass) of the aqueous composition.
• Copper ions in an aqueous composition can be generated by mixing a copper compound as a copper ion source with other components.
• the type of copper ion source is not particularly limited as long as it is a copper compound capable of supplying copper ions in the aqueous composition.
• copper sulfate such as cupric sulfate
• copper chloride such as cupric chloride, copper tetrafluoroborate, cupric bromide, oxidation.
• copper sulfate or copper chloride is preferable, and cupric sulfate or cupric chloride is more preferable, from the viewpoints of more effective and reliable effect of the present invention, ease of handling, and economy. Copper sulfate is more preferred. These may be used alone or in combination of two or more.
• the copper ions contained in the aqueous composition cause a substitution reaction with nickel and chromium, which are components of stainless steel, in the roughening treatment, and then the roughened shape is formed by removing the substitution reaction product derived from the copper ions. Is presumed to be obtained. Further, in the quality of stainless steel after roughening treatment, particularly in an aqueous composition used for treating a stainless steel foil having a small thickness, as will be described later, extremely thin regions and pinholes are prevented from occurring. Therefore, it is preferable to adjust the content of copper ions.
• the concentration of copper ions contained in the aqueous composition is 3% by mass or less, preferably 2% by mass or less, less than 1.5% by mass or 1.5% by mass or less, and more preferably 1.2. It may be 0.75% by mass or less, 0.5% by mass or less, and less than 0.25% by mass, and may be 0.75% by mass or less, or 1.0% by mass or less.
• the concentration range of copper ions is 0 to 3% by mass, preferably 0 to 2% by mass, more preferably 0 to 1.5% by mass, and further preferably 0.1 to 1.5% by mass. It may be 0.2 to 1.5% by mass.
• the lower limit of the concentration of copper ions in the aqueous composition is 0% by mass based on the total amount (total mass) of the aqueous composition, but for example, 0.00001% by mass (0.1% by mass), 0. 0001% by mass (1% by mass), 0.001% by mass, 0.01% by mass, 0.02% by mass, 0.03% by mass, 0.05% by mass, 0.07% by mass, 0.1% by mass May be.
• the upper limit of the concentration of copper ions in the aqueous composition is, for example, 3% by mass, 2.5% by mass, 2% by mass, 1.7% by mass, and 1.5% by mass based on the total amount of the aqueous composition.
• the range of the concentration of copper ions is a range in which the above-mentioned lower limit value and upper limit value are appropriately combined, for example, 0.0001 to 3% by mass, 0.001 to 3% by mass, 0.01 to 2% by mass, 0. 01 to 1.7% by mass, 0.01 to 1.5% by mass, 0.02 to 1% by mass, 0.03 to 0.25% by mass, 0.03 to 0.20% by mass, 0.05 to It can be appropriately selected from 0.15% by mass, 0.05 to 0.12% by mass, and the like.
• the effects of the present invention tend to be more preferably achieved.
• the concentration of copper ions in the aqueous composition is too high, pinholes and extremely thin regions are likely to occur in the roughened stainless steel, and if the concentration of copper ions is too low, the roughening treatment is performed. It may not proceed efficiently.
• the aqueous composition of the present invention may contain an additive as a component other than the above-mentioned hydrogen peroxide, copper ion, and halide ion as long as the effect of the present invention is exhibited.
• the additive include a heterocyclic nitrogen compound (azole compound), an organic solvent and the like. These may be used alone or in combination of two or more.
• examples of the additive include a surfactant, a pH adjuster and the like, but these should not be included in the aqueous composition of the present invention.
• the concentration of the additive that may be contained in the aqueous composition is preferably 10% by mass or less, more preferably 5.0% by mass or less, and even more preferably 2.0% by mass or less. Particularly preferably, it is 1.0% by mass or less.
• the aqueous composition of the present invention may contain water, and preferably contains water.
• the water is not particularly limited, but is preferably water from which metal ions, organic impurities, particles, etc. have been removed by distillation, ion exchange treatment, filter treatment, various adsorption treatments, etc., more preferably pure water, and ultrapure water. Especially preferable.
• the content of water in the aqueous composition of the present invention is the balance of each of the above-mentioned components and the additives described in detail later, and is not particularly limited, but is 50 to 98 based on the total amount (total mass) of the aqueous composition.
• the mass% is preferable, more preferably 60 to 95% by mass, still more preferably 75 to 93% by mass, and particularly preferably 85 to 90% by mass.
• the aqueous composition of the present invention is preferably a solution, and preferably does not contain a component insoluble in the composition which is the solution, for example, solid particles such as abrasive particles.
• the aqueous composition containing each of the above components is considered to function as follows in the roughening treatment of the stainless steel surface.
• Halide ions are responsible for pitting the oxide film normally formed on the surface of stainless steel.
• the copper ion has an action of causing a substitution reaction with nickel and chromium, which are components of the stainless steel, and then the substitution reaction product derived from the copper ion is removed, and Rz is generated on the surface of the stainless steel. It is considered that large unevenness, that is, a roughened shape is formed.
• hydrogen peroxide serves to remove the substitution reaction product derived from the copper ion after the above-mentioned substitution reaction. Then, by using an aqueous composition containing copper ions or the like whose content is adjusted to an appropriate range, it is possible to prevent the occurrence of extremely thin regions and pinholes in the roughened stainless steel, especially the stainless steel foil. can.
• the aqueous composition of the present invention the above-mentioned hydrogen peroxide-containing component, halide ion supply component, and water, and if necessary, a copper ion supply component and other components are added and stirred until uniform.
• the properties of the aqueous composition are not particularly limited, but the pH value is preferably ⁇ 1.0 to 4.0, more preferably ⁇ 0.5 to 3.0, and even more preferably. It is ⁇ 0.25 to 2.5, and particularly preferably ⁇ 0.1 to 2.0, 0.0 to 1.5, 0.005 to 1.0 or 0.01 to 0.5.
• the pH value can be measured by the method described in Examples.
• the roughening treatment method for roughening the surface of stainless steel of the present invention includes a roughening treatment step of roughening the surface of stainless steel using the above-mentioned aqueous composition.
• roughening the surface of stainless steel using the aqueous composition means bringing the aqueous composition used for the treatment into contact with the surface of the stainless steel.
• the method for roughening the stainless steel of the present invention includes at least a step of bringing the aqueous composition into contact with the surface of the stainless steel.
• the roughening treatment step is a step of bringing the above-mentioned aqueous composition into contact with the stainless steel to be roughened.
• the temperature of the roughening treatment is preferably 20 to 60 ° C, more preferably 25 to 55 ° C, and particularly preferably 30 to 50 ° C.
• the method for roughening stainless steel of the present invention is excellent in that the surface of stainless steel is roughened even at room temperature of 25 ° C. even if the temperature is not so high.
• the temperature of the roughening treatment refers to the temperature at which the aqueous composition is brought into contact with the surface of the stainless steel, particularly the liquid temperature of the aqueous composition which is brought into contact with the surface of the stainless steel.
• the roughening treatment time is preferably 30 seconds to 120 seconds, more preferably 40 seconds to 100 seconds, and particularly preferably 50 seconds to 90 seconds. ..
• the method for roughening stainless steel of the present invention is excellent in that the roughening of stainless steel progresses even if it does not take a very long time.
• the roughening treatment time refers to the time for contacting the aqueous composition with the surface of the stainless steel. For example, the time for immersing the stainless steel in the aqueous composition, the time from spraying the aqueous composition on the surface of the stainless steel to the time for removing the aqueous composition with water or the like.
• the method of contacting the aqueous composition with the surface of the stainless steel is not particularly limited, and for example, the aqueous composition is brought into contact with the stainless steel by a form such as dropping or spraying (spraying), or the stainless steel is used.
• a method of immersing in an aqueous composition or the like can be adopted.
• any method may be adopted.
• a method of spraying an aqueous composition onto stainless steel processed into a specific shape to obtain a roughened stainless steel or installing an aqueous composition dropping device, a spraying device, or a dipping device between stainless steel foil rolls.
• the aqueous composition is supplied by passing through the vicinity of the above-mentioned device, and coarsely prepared.
• examples thereof include a method of winding a stainless steel foil that has been subjected to a chemical treatment to obtain a roll.
• the stainless steel roughened in the roughening treatment step may be subjected to a treatment such as washing with water.
• the roughened stainless steel also referred to as roughened stainless steel in the present specification, and stainless steel foil (film or sheet) is also included in the stainless steel.
• the maximum height (Rz) of the surface can be 1.0 ⁇ m or more, 2.0 ⁇ m or more, or 3.0 ⁇ m or more. That is, in the roughening treatment method for stainless steel of the present invention, even in the stainless steel immediately after the roughening treatment step, all the treatments such as washing the stainless steel with water are completed, and the finally obtained roughening is completed.
• the maximum height (Rz) of the surface can be 1.0 ⁇ m or more, 2.0 ⁇ m or more, 2.5 ⁇ m or more and 3.0 ⁇ m or more, or 3.5 ⁇ m or more. In this way, the point that the targeted roughening level is achieved immediately after the roughening treatment process or on the surface of the stainless steel of the final product is the same for the following surface roughness parameters (including Ra). be.
• the maximum height (Rz) of the surface of the roughened stainless steel is preferably 1.0 ⁇ m or more, and more preferably 1.5 ⁇ m or more after the roughening treatment step. Preferably, it may be 2.0 ⁇ m or more, 2.5 ⁇ m or more, or 3.0 ⁇ m or more.
• the upper limit of the maximum height (Rz) of the roughened stainless steel surface is not particularly limited, but is, for example, 5.0 ⁇ m or less, 4.0 ⁇ m or less, or 3.0 ⁇ m or less. May be.
• the maximum surface height (Rz) of the stainless steel that has not been roughened (also referred to as untreated stainless steel in the present specification) is not particularly limited, but for example. , 0.2 to 2.0 ⁇ m, etc., and about 0.5 to 1.5 ⁇ m.
• the maximum height (Rz) of the roughened stainless steel surface is larger than the value of the maximum height (Rz) of the untreated stainless steel surface after the roughening treatment step.
• the value can be 0.1 ⁇ m or more, preferably 0.3 ⁇ m or more larger than that of untreated stainless steel, more preferably 0.5 ⁇ m or more, and 1.0 ⁇ m or more. A large value is more preferable, and a value larger than 1.5 ⁇ m may be used.
• the arithmetic mean roughness (Ra) of the surface of the roughened stainless steel can be 0.1 ⁇ m or more after the roughening treatment step.
• the arithmetic mean roughness (Ra) of the surface of the roughened stainless steel is preferably 0.15 ⁇ m or more, or 0.2 ⁇ m or more after the roughening treatment step. It is more preferably possible to make it 0.3 ⁇ m or more, or 0.4 ⁇ m or more, and it may be 0.5 ⁇ m or more or 0.6 ⁇ m or more.
• the upper limit of the arithmetic mean roughness (Ra) of the surface of the roughened stainless steel is not particularly limited, but is, for example, 1.0 ⁇ m or less, 0.8 ⁇ m or less, or 0.7 ⁇ m or less. There may be.
• the arithmetic mean roughness (Ra) of the untreated stainless steel is not particularly limited, but is, for example, 0.03 to 1.0 ⁇ m, preferably 0.05 to 0.5 ⁇ m. ..
• the arithmetic average roughness (Ra) of the surface of the roughened stainless steel is the arithmetic average roughness (Ra) of the flat surface of the untreated stainless steel after the roughening treatment step. It is possible to make the value 0.02 ⁇ m or more larger than that, preferably 0.04 ⁇ m or more larger than the untreated stainless steel, and more preferably 0.10 ⁇ m or more. A value larger than 20 ⁇ m is more preferable, a value larger than 0.30 ⁇ m is particularly preferable, and a value larger than 0.40 ⁇ m or 0.50 ⁇ m may be used.
• the above-mentioned maximum height (Rz) and arithmetic mean roughness (Ra) are calculated according to JIS B 0601-2001.
• the device used for the measurement is not particularly limited, but for example, a laser microscope can be used.
• the maximum height (Rz) after the roughening treatment step after removing the precipitate from the surface of the roughened stainless steel in which the precipitate was generated after the roughening treatment by a physical means such as an adhesive tape.
• the value of arithmetic mean roughness (Ra) can be measured.
• such physical means are not always practical as part of the manufacturing process.
• the etching rate of the stainless steel in the roughening treatment step is not particularly limited, but is, for example, 0.1 ⁇ m / min or more, preferably 0.5 ⁇ m / min or more, and more preferably 0.7 ⁇ m / min.
• the above more preferably 1.0 ⁇ m / min or more, 1.5 ⁇ m / min or more, 2.0 ⁇ m / min or more, 2.5 ⁇ m / min or more, 3.0 ⁇ m / min or more, or 3.5 ⁇ m / min or more. May be.
• a substantially one-step treatment that is, a roughening treatment in which the aqueous composition of the present invention is brought into contact with the surface of the stainless steel to be treated. It is possible to obtain stainless steel with enlarged surface irregularities only by further performing appropriate cleaning (for example, water cleaning) according to the above. Further, as described above, since the treatment conditions in the roughening treatment are mild and the required time is short, the roughening treatment of stainless steel can be efficiently performed according to the present invention.
• the type of stainless steel to be roughened by the aqueous composition of the present invention is not particularly limited, and examples thereof include the following. That is, SUS304, SUS316, SU defined by the JISG4305 standard. Chromium-nickel stainless steel containing S321, SUS347, and SUS329J1; ferritic stainless steel (chrome stainless steel) containing SUS405, SUS430, SUS434, SUS444, SUS447, and SUSXM27; and precipitation hardening stainless steel containing SUS630, SUS631, and SUH660 (chromium-nickel). Stainless steel) etc. Of the above-mentioned stainless steels, SUS304 and SUS444 are more preferable as targets for the roughening treatment with the aqueous composition.
• the maximum height (Rz) on the surface of the roughened stainless steel is, for example, 1.0 ⁇ m or more, preferably 1.5 ⁇ m or more, and 2.0 ⁇ m or more, 2.5 ⁇ m or more. , Or may be 3.0 ⁇ m or more.
• the upper limit of the maximum height (Rz) of the roughened stainless steel surface is not particularly limited, but is, for example, 5.0 ⁇ m or less, 4.0 ⁇ m or less, or 3.0 ⁇ m or less. May be.
• the arithmetic mean roughness (Ra) of the surface of the roughened stainless steel is, for example, 0.1 ⁇ m or more, preferably 0.15 ⁇ m or more, or 0.2 ⁇ m or more, preferably 0.3 ⁇ m or more, or 0.4 ⁇ m. The above is more preferable, and it may be 0.5 ⁇ m or more.
• the upper limit of the arithmetic mean roughness (Ra) of the surface of the roughened stainless steel is not particularly limited, but is, for example, 1.0 ⁇ m or less, 0.8 ⁇ m or less, or 0.7 ⁇ m or less. There may be.
• the size, thickness, and shape of the stainless steel to be roughened are not particularly limited, and for example, it can be applied to stainless steel foil.
• the thickness of the stainless steel to which the roughening treatment method of the present invention is applied is not particularly limited, but is, for example, 1 ⁇ m or more and 500 ⁇ m or less, preferably 5 ⁇ m or more and 100 ⁇ m or less.
• the thickness of the stainless steel is more preferably 15 ⁇ m or less.
• the region of the stainless steel to be roughened has at least a portion having a thickness of 15 ⁇ m or less.
• the thickness of all regions of the stainless steel to be roughened may be 15 ⁇ m or less.
• the thickness of the roughened portion is substantially uniform (excluding fine irregularities on the surface) by the roughening treatment using the aqueous composition having the above-mentioned components. ) Roughened stainless steel can be obtained, and it is possible to prevent the occurrence of extremely thin regions and pinholes.
• the thickness of the stainless steel or the stainless steel foil to be roughened may be, for example, 12 ⁇ m or less, 10 ⁇ m or less, 8 ⁇ m or less, and 6 ⁇ m or less.
• stainless steel or stainless steel foil having a thickness of 20 ⁇ m or less, 30 ⁇ m or less, 50 ⁇ m or less, etc. may be subject to the roughening treatment.
• the lower limit of the thickness of the stainless steel or the stainless steel foil is not particularly limited, but is, for example, 1.0 ⁇ m.
• the thickness of the stainless steel or the stainless steel foil may be, for example, 1.5 ⁇ m or more, 2.0 ⁇ m or more, 3.0 ⁇ m or more, 5.0 ⁇ m or more.
• the region of the stainless steel or the stainless steel foil where the roughening treatment is performed has at least a portion in the above-mentioned thickness range. Further, it is preferable that the thickness of all the regions to be roughened in the stainless steel is within the above range, and further, regardless of the region to be roughened, the entire region of the stainless steel is formed. It is preferably within the above range.
• the method for producing stainless steel of the present invention has at least the above-mentioned roughening treatment step. According to the method for producing stainless steel of the present invention, it is possible to produce stainless steel having a surface that is rougher than that before the roughening treatment, that is, has a surface in which irregularities are enlarged more than the surface before the treatment.
• the stainless steel that is the target of the stainless steel manufacturing method of the present invention is described in the above [3. Stainless steel] as described in the column.
• the maximum height (Rz) and arithmetic mean roughness (Ra) of the surface of the roughened stainless steel obtained by the method for producing stainless steel of the present invention are described in the above [3. Stainless steel] as described in the column.
• the roughened stainless steel obtained by the method for producing stainless steel of the present invention is, for example, a collector foil for batteries such as solid-state batteries and lithium-ion batteries, a solar cell base material, a flexible substrate for electronic devices, and a power storage device. It can be used as a substrate, a carrier such as an exhaust gas purification catalyst, an electromagnetic wave shielding member, and a heat radiating member.
• the roughened stainless steel foil obtained by the method for producing stainless steel of the present invention is suitably used as, for example, a current collector foil for a battery.
• a stainless steel (foil) having a thickness of 10 ⁇ m, a length and a width of 30 mm ⁇ 30 mm, and a material of SUS304 was prepared.
• the Rz of the stainless steel foil and Ra of the stainless steel foil measured according to the above (measurement of the surface roughness of the stainless steel foil) were 1.26 ⁇ m and Ra was 0.08 ⁇ m.
• the surface roughness values of the untreated stainless steel foil are shown in Table 1 below as a reference example.
• the amount of hydrogen hydrogen finally becomes 0.5% by mass (1.7 g of 60 wt% hydrogen peroxide aqueous solution), and 34 mass% (68.6 g) of 35 wt% hydrochloric acid aqueous solution.
• Each added aqueous composition was prepared.
• the concentration of the halide ion (Cl ⁇ ) derived from hydrochloric acid in this composition was 12% by mass based on the total amount of the aqueous composition.
• the stainless steel foil was immersed in the aqueous composition at a liquid temperature of 35 ° C. for 60 seconds. Then, the stainless steel foil after immersion was thoroughly washed with ultrapure water and then sufficiently dried to obtain a surface-treated foil.
• the obtained surface-treated foil was measured according to the above (measurement of the surface roughness of the stainless steel foil), the Rz value was 1.17 ⁇ m and the Ra value was 0.12 ⁇ m. Further, when the surface shape was visually observed according to the above (confirmation of the presence or absence of pinholes), no pinholes (fine through holes) were observed, and the evaluation was "good".
• Example 1 2.0 g of copper sulfate pentahydrate was further added to the aqueous solution to obtain the composition shown in Table 1, and the stainless steel foil was roughened in the same manner as in Example 1. A surface treated foil was obtained. The concentration of copper ions (Cu 2+ ) derived from copper sulfate in this aqueous composition was 0.25% by mass based on the total amount of the aqueous composition. Table 1 shows the results of the Rz value, Ra value, etc. of the obtained surface-treated foil. [Examples 3 to 6, 12 to 15 and Comparative Example 1]
• a stainless steel foil was used in the same manner as in Example 1 except that the concentrations of at least one of hydrogen peroxide, chloride ion and copper ion (Cu 2+ ) in the aqueous composition were changed to the compositions shown in Table 1. Roughening treatment was performed to obtain a surface-treated foil. Table 1 shows the results of the Rz value, Ra value, etc. of the obtained surface-treated foil. [Examples 7 to 11]
• the surface of stainless steel can be sufficiently and efficiently roughened in a short time with a sufficient number of steps. Further, it is possible to realize stainless steel of good quality, particularly one having a uniform thickness and free from defects such as pinholes. Then, if stainless steel having a rough surface while maintaining a good appearance, particularly stainless steel foil, is used for a battery current collector foil, an automobile component housing, etc., a dielectric substance or an organic substance is effectively adhered or organic. , Can be retained. Further, as a member for dissipating heat, stainless steel having a roughened surface can be preferably used. Therefore, the present invention has industrial applicability in the field of surface roughening treatment of material members, for example, stainless steel used in the above products.

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