CN115362284A - Method for producing rust-proof member - Google Patents
Method for producing rust-proof member Download PDFInfo
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- CN115362284A CN115362284A CN202180026107.1A CN202180026107A CN115362284A CN 115362284 A CN115362284 A CN 115362284A CN 202180026107 A CN202180026107 A CN 202180026107A CN 115362284 A CN115362284 A CN 115362284A
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- 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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
- C23C22/53—Treatment of zinc or alloys based thereon
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- 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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/24—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing hexavalent chromium compounds
- C23C22/30—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing hexavalent chromium compounds containing also trivalent chromium
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- 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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
- C23C22/50—Treatment of iron or alloys based thereon
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- 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
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/10—Use of solutions containing trivalent chromium but free of hexavalent chromium
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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
A reactive chemical conversion treatment liquid which is characterized by containing colloidal silica, a water-soluble trivalent chromium-containing substance, and a water-soluble high-pKa organic acid-containing substance exemplified by a hydroxymonocarboxylic acid, and in a preferred embodiment, a water-soluble film-forming metal-containing substance, wherein the pH of the chemical conversion treatment liquid is 3.0 or more, and the reactive chemical conversion treatment liquid is capable of forming a chemical conversion film containing Si.
Description
Technical Field
The present invention relates to a method for manufacturing a rust-proof member.
Background
Patent document 1 describes a corrosion-resistant substrate having a surface layer of a substrate to be treated provided with a zinc or zinc alloy plating layer, the surface layer including a lower layer containing Cr and a layer containing SiO 2 The two-layer structure chemical conversion coating film obtained by the one-liquid treatment.
Documents of the prior art
Patent document
Patent document 1: japanese patent No. 3620510
Disclosure of Invention
Problems to be solved by the invention
An object of the present invention is to provide a reactive chemical conversion treatment liquid capable of forming a chemical conversion coating film containing Si as described in patent document 1, and a method for producing a rust-proof member using the chemical conversion treatment liquid.
Means for solving the problems
In order to solve the above problems, one aspect of the present invention is a method for producing a rust-preventive member, including a chemical conversion treatment step of bringing a chemical conversion treatment liquid into contact with a member to be treated containing zinc on a surface thereof, and then cleaning the member to be treated to form a chemical conversion coating film on the member to be treated, the chemical conversion treatment liquid including: colloidal silicon dioxide; the trivalent chromium-containing water-soluble substance is an ionic substance containing trivalent chromium; and a water-soluble substance containing a high pKa organic acid, wherein the chemical conversion treatment liquid has a pH of 3.0 or more and 4.5 or less in a state before being brought into contact with the member to be treated, and the high pKa organic acid contains glycolic acid (except for the case where at least one selected from the group consisting of allyl amine, polyallyl amine, an aromatic sulfonic acid-formaldehyde condensate, and a derivative thereof is contained). That is, the chemical conversion treatment liquid does not contain allylamine, polyallylamine, aromatic sulfonic acid-formaldehyde condensate, and derivatives thereof as active ingredients.
In the above production method, the chemical conversion treatment liquid may satisfy at least one of the following requirements.
The content of the colloidal silica is 2g/L to 25 g/L.
The trivalent chromium-containing water-soluble substance has a trivalent chromium-equivalent content of 1g/L to 6 g/L.
The high pKa organic acid-equivalent content of the water-soluble substance containing a high pKa organic acid is 0.2 or more and 2 or less in terms of a molar ratio to the trivalent chromium-equivalent content of the water-soluble substance containing trivalent chromium.
And a water-soluble substance containing a film-forming metal, wherein the water-soluble substance containing a film-forming metal is a water-soluble substance containing a metal ion capable of forming a film by an interaction with oxygen.
The ratio of the content (unit: g/L) of colloidal silica to the content (unit: g/L) of the high-pKa organic acid-containing water-soluble substance in terms of high-pKa organic acid (colloidal silica/high-pKa organic acid) is in the range of 0.5 to 10.
The chemical conversion treatment liquid further contains a water-soluble substance containing a low pKa organic acid, the water-soluble substance containing a low pKa organic acid being an organic acid having a lowest pKa of 1.27 or more and less than 3.5, and the molar ratio of the low pKa organic acid-equivalent content of the water-soluble substance containing a low pKa organic acid to the high pKa organic acid-equivalent content of the water-soluble substance containing a high pKa organic acid is 1 or less.
Preferably, in the above-described manufacturing method, the member to be processed is formed by forming a zinc-based plating layer on a base material.
In the above production method, the base material may be a cast product.
Effects of the invention
According to the present invention, there are provided a reactive chemical conversion treatment liquid capable of forming a chemical conversion coating film containing Si, and a method for producing a rust-proof member using the chemical conversion treatment liquid.
Detailed Description
Hereinafter, embodiments of the present invention will be described.
A chemical conversion treatment liquid according to one embodiment of the present invention contains colloidal silica, a trivalent chromium-containing water-soluble substance, a film-forming metal-containing water-soluble substance, and a high pKa organic acid-containing water-soluble substance, and has a pH of 3.0 or more. Preferably, the chemical conversion treatment liquid according to the present embodiment further contains a water-soluble substance containing a film-forming metal.
The colloidal silica is silica dispersed in a chemical conversion treatment liquid in a colloidal form, and typically has a primary particle diameter of a sub-nanometer order to a sub-micrometer order. As described below, in the chemical conversion treatment liquid of the present embodiment, a high pH region in which the pH tends to increase is generated in the vicinity of the surface of the member to be treated. Therefore, the colloidal silica contained in the chemical conversion treatment liquid near the surface of the member to be treated is easily gelled. In the region including the gel in the vicinity of the surface of the member to be treated, the colloidal silica is gelled to reduce the substance transfer to the main region, and therefore the chemical conversion treatment liquid is easily maintained in a high pH state. Therefore, zinc dissolved from the member to be treated is less likely to diffuse into the bulk region and is likely to stay in the high pH region. Therefore, in the chemical conversion treatment liquid of the present embodiment, zinc dissolved from the member to be treated is likely to become a constituent element of the chemical conversion coating in the form of hydroxide.
Further, since colloidal silica that diffuses and moves from the main body region to the high pH region rapidly gels due to the high pH value in the high pH region and the mobility decreases, a thick chemical conversion coating film is easily formed by using the reactive chemical conversion treatment liquid of the present embodiment. The chemical conversion coating formed using a general reaction type chemical conversion treatment liquid has a thickness of less than 100nm, but the chemical conversion coating of the present embodiment is easily 200nm or more, and the chemical conversion coating can be grown to a thickness of about 1 μm by adjusting the contact time between the member to be treated and the chemical conversion treatment liquid.
The content of colloidal silica in the chemical conversion treatment liquid of the present embodiment is preferably 2g/L to 25 g/L. If the content of the colloidal silica is too small, the rate of formation of the chemical conversion coating may be slow, or the corrosion resistance of the chemical conversion coating may be reduced. If the content of the colloidal silica is too large, the viscosity of the chemical conversion treatment liquid may be increased, or the lifetime of the chemical conversion treatment liquid may be shortened. From the viewpoint of ensuring the stability of the chemical conversion treatment liquid and the corrosion resistance of the chemical conversion coating, the content of colloidal silica in the chemical conversion coating is preferably 4g/L or more and 20g/L or less in some cases, and more preferably 6g/L or more and 20g/L or less in some cases.
The water-soluble material containing trivalent chromium contains trivalent chromium (Cr) 3+ ) The ionic substance of (1). The trivalent chromium content (hereinafter referred to as "trivalent chromium content") of the trivalent chromium-containing water-soluble substance is preferably 1g/L to 6 g/L. If the trivalent chromium content is too small, the rate of formation of the chemical conversion coating may be reduced, or the corrosion resistance of the chemical conversion coating may be reduced. If the trivalent chromium content is too high, the viscosity of the chemical conversion treatment liquid may increase, or the lifetime of the chemical conversion treatment liquid may decrease. From the viewpoint of ensuring the stability of the chemical conversion treatment liquid and the corrosion resistance of the chemical conversion coating, the trivalent chromium content in the chemical conversion coating is preferably 1g/L or more and 5g/L or less, and more preferably 1.2g/L or more and 4.1g/L or less.
The water-soluble substance containing a high pKa organic acid is a water-soluble substance containing an organic acid having a lowest pKa of 3.5 or more (high pKa organic acid), and includes the high pKa organic acid, an ion of the high pKa organic acid, and a complex including the ion. Since the water-soluble substance containing an organic acid having a high pKa has a high pH buffering range due to its high pKa, the chemical conversion treatment liquid located in the region near the surface of the member to be treated is relatively easy to maintain the pH increase due to the dissolution of the member to be treated. One reason for this is that a high pH region is formed when the chemical conversion treatment liquid of the present embodiment is used. Specifically, in the high pH region, the chemical conversion treatment liquid may have a pH of about 6 or more at which the colloidal silica is easily gelled. From the viewpoint of improving the stability of the chemical conversion treatment liquid, the lowest pKa of the high pKa organic acid is sometimes preferably 4.5 or less, and sometimes more preferably 4.0 or less.
Further, since the water-soluble substance containing an organic acid having a high pKa has a high pKa, it is not easy to form a complex with zinc ions generated by dissolution of the member to be treated. Therefore, zinc ions generated in the chemical conversion treatment liquid near the surface of the member to be treated are less likely to be complexed, and are likely to exist in the state of zinc hydrate ions. Therefore, in the chemical conversion treatment using the chemical conversion treatment liquid of the present embodiment, zinc ions generated by dissolution of the member to be treated are likely to become hydroxides and become components of the chemical conversion coating.
Specific examples of the high pKa organic acid, which is a water-soluble substance containing the high pKa organic acid, include hydroxymonocarboxylic acids such as glycolic acid (3.83), lactic acid (3.86), (±) -3-hydroxybutyric acid (4.70), and glyceric acid (3.64). The water-soluble substance containing an organic acid having a high pKa may be one or more kinds of organic acids having a high pKa. In view of the difficulty of interaction with zinc ions, it is preferable that the organic acid of the water-soluble substance containing an organic acid with a high pKa comprises lactic acid or glycolic acid.
The content of the water-soluble substance containing an organic acid with a high pKa in the chemical conversion treatment liquid according to the present embodiment is set according to the type of the organic acid with a high pKa, the required properties of the film (corrosion resistance, film appearance, film formation rate), and the like. By way of non-limiting example, the content of the high pKa organic acid in terms of the water-soluble substance containing the high pKa organic acid is preferably 0.2 or more and 2 or less, more preferably 0.25 or more and 2 or less, and particularly preferably 0.5 or more and 1.2 or less in terms of a molar ratio (high pKa organic acid/trivalent chromium) to the content of the trivalent chromium. When glycolic acid is contained as the high pKa organic acid, the glycolic acid equivalent content of the water-soluble substance containing a high pKa organic acid containing glycolic acid is preferably 1g/L or more and 10g/L or less, more preferably 2g/L or more and 7g/L or less, and particularly preferably 3g/L or more and 6g/L or less. In this case, the water-soluble substance containing an organic acid with a high pKa may contain an organic acid with a high pKa other than glycolic acid (for example, lactic acid).
The ratio of the content (unit: g/L) of the colloidal silica to the content (unit: g/L) of the high pKa organic acid-containing water-soluble substance in terms of the high pKa organic acid (colloidal silica/high pKa organic acid) is preferably in the range of 0.5 to 10, and more preferably 0.6 or more and 9 or less. If the ratio is too large, the effect of the water-soluble substance containing an organic acid having a high pKa may not be obtained easily. If the ratio is too small, the rate of formation of the chemical conversion coating may be slow, and the film thickness may become thin.
The chemical conversion treatment liquid of the present embodiment may contain, in addition to the water-soluble substance containing an organic acid with a high pKa, a water-soluble substance containing an organic acid with a low pKa, that is, a water-soluble substance containing an organic acid with a low pKa having a lowest pKa of less than 3.5. By containing a water-soluble substance containing an organic acid having a low pKa, the appearance (particularly, the degree of brightness) of the chemical conversion coating film may be adjusted. Examples of the low pKa organic acid-containing water-soluble substance include oxalic acid (lowest pKa: 1.27), succinic acid (lowest pKa: 3.09), malic acid (lowest pKa: 3.4), and the like. The molar ratio of the content of the low pKa organic acid in terms of organic acid equivalent to the content of the high pKa organic acid in terms of organic acid equivalent to the water-soluble substance containing an organic acid with a high pKa (organic acid molar ratio) is preferably 3 or less. From the viewpoint of more stably improving the corrosion resistance, the organic acid molar ratio is preferably 1 or less, more preferably 1/2 or less, still more preferably 1/3 or less, and particularly preferably 1/10 or less.
The film-forming metal-containing water-soluble substance is a water-soluble substance containing metal (film-forming metal) ions capable of forming a film by interaction with oxygen or the like. Specifically, examples of the film-forming metal include Ti, al, V, nb, ta, W, zr, and the like. As more preferable comparative forming metals, ti and Al are exemplified. The type of the film-forming metal constituting the water-soluble substance containing the film-forming metal contained in the chemical conversion treatment liquid may be one type or a plurality of types.
The content of the water-soluble substance containing the film-forming metal in the chemical conversion treatment liquid of the present embodiment is set according to the type of the film-forming metal, the required properties of the film (corrosion resistance, film appearance, film formation speed, and the like), and the like. By way of non-limiting example, when the comparative forming metal is Ti and Al, the Ti content of the Ti-containing film-forming metal-containing water-soluble substance is preferably 0.03g/L to 0.45g/L in terms of Ti, more preferably 0.05g/L to 0.30g/L, and particularly preferably 0.06g/L to 0.20 g/L. In this case, the Al content of the Al-containing film-forming metal-containing water-soluble substance is preferably 2mg/L to 50mg/L, more preferably 3mg/L to 30mg/L, and particularly preferably 4mg/L to 15 mg/L.
The chemical conversion treatment liquid of the present embodiment may contain, in addition to the above-described essential components, the following optional additional components. Examples of such an optional additive component include a film-forming element-containing substance containing one or more elements selected from the group consisting of P, B, C, S, li, ca, mg, fe, ni, co, cu, si, zn, al, sn, bi, and lanthanoids. The content of the film-forming element-containing substance in terms of element can be appropriately set within a range in which the purpose of containing the element is achieved.
The chemical conversion treatment liquid of the present embodiment has a pH of 3.0 or more. Since the chemical conversion treatment liquid contains the water-soluble substance containing an organic acid with a high pKa in a high pH buffer range as described above in addition to a relatively high pH of the chemical conversion treatment liquid, the chemical conversion treatment liquid of the present embodiment easily forms a high pH region in the vicinity of the surface of the member to be treated. Therefore, the colloidal silica contained in the chemical conversion treatment liquid of the present embodiment is likely to gel in the vicinity of the surface of the member to be treated, and a thick chemical conversion coating film is likely to be formed.
The pH of the chemical conversion treatment solution of the present embodiment can be adjusted by using an inorganic acid such as hydrochloric acid or nitric acid, an organic acid such as acetic acid, an inorganic base such as sodium hydroxide or potassium hydroxide, an organic base such as an amine, or the like. The upper limit of the pH of the chemical conversion treatment liquid of the present embodiment is not set as long as the chemical conversion treatment liquid functions. The pH of the chemical conversion treatment liquid of the present embodiment may be preferably 4.5 or less, and may be more preferably 4.0 or less, from the viewpoint of ensuring the ease of formation of a chemical conversion coating and the stability of the chemical conversion treatment liquid.
A method for producing a rust-preventive member according to an embodiment of the present invention uses the chemical conversion treatment liquid according to the above-described embodiment, and includes a plating step and a chemical conversion treatment step described below.
In the plating step, a zinc-based plating layer is formed on a base material to obtain a member to be treated that includes the base material and the zinc-based plating layer. In the present specification, "zinc-based plating" refers to a generic term of zinc plating and zinc-based alloy plating. The base material is made of, for example, an iron-based material, and is manufactured by rolling, casting, extrusion, etc., and is shaped by rolling, cutting, pressing, etc., machining, forming, etc. The zinc plating layer may be formed by electroplating or by other methods.
The chemical conversion coating formed from the chemical conversion treatment liquid of the present embodiment is less likely to be affected by the shape (height difference, unevenness, and the like) and the surface properties (surface roughness, and the like) of the substrate. As described above, since the chemical conversion treatment liquid of the present embodiment has a relatively high pH, the amount of zinc-based plating is reduced as compared with the case of using a normal chemical conversion treatment liquid having a pH of less than 3 (specifically, 2.0 to 2.5). Therefore, the chemical conversion coating can be stably formed even in the following cases: since the base material has a shape with a level difference or has a large variation in surface properties such as a high surface roughness, the member to be treated has a portion with a small thickness of the zinc-based plating layer. As a specific example of such a base material, a cast product can be cited. If the thickness of the zinc-based plating layer is 10 μm or more, the possibility of local corrosion resistance degradation can be stably avoided. When the thickness of the zinc-based plating layer is 5 μm or more, a local decrease in corrosion resistance can be suppressed.
As described above, the chemical conversion coating formed from the chemical conversion treatment liquid of the present embodiment is less susceptible to the influence (thickness, composition) of the zinc plating system, and therefore the chemical conversion coating of the present embodiment is less susceptible to the influence of the composition of the plating liquid used to form the zinc plating system. In the case of forming a zinc plating system, a brightener (a primary brightener, a secondary brightener) may be added to the plating solution from the viewpoint of adjusting the film thickness and the surface properties (e.g., the degree of brightness) of the zinc plating layer to be formed. The brightener is consumed when the bath is used, and thus the concentration of brightener in the bath constantly fluctuates. In order to suppress the fluctuation range, the plating solution is used while adding a brightener to the plating solution periodically. Since the chemical conversion coating film of the present embodiment is less susceptible to the composition of the plating solution, it is not necessary to strictly control the brightener concentration.
The chemical conversion treatment step includes bringing the member to be treated into contact with the chemical conversion treatment liquid of the present embodiment described above, and then cleaning the member to be treated to form a chemical conversion coating on the member to be treated. Examples of the method of contacting the chemical conversion treatment liquid with the member to be treated include immersing the member to be treated in the chemical conversion treatment liquid, spraying the chemical conversion treatment liquid onto the member to be treated, and the like.
In the reaction type chemical conversion treatment, in general, zinc is dissolved from the surface of the member to be treated, and thus the tendency of the fluidity of the chemical conversion treatment liquid in the vicinity of the surface of the member to be treated to decrease is not significant. Therefore, by the chemical conversion treatment, the mutual diffusion of the chemical conversion treatment liquid near the surface of the member to be treated and the chemical conversion treatment liquid of the main body continuously occurs. Therefore, even if the pH of the chemical conversion treatment liquid near the surface increases due to dissolution of zinc from the surface of the member to be treated, the chemical conversion treatment liquid mainly diffuses near the surface, and the increase in pH of the chemical conversion treatment liquid near the surface is restricted.
In contrast, in the chemical conversion treatment liquid of the present embodiment, as described above, zinc dissolves from the surface of the member to be treated and the colloidal silica is gelled, so that the fluidity of the chemical conversion treatment liquid in the vicinity of the surface of the member to be treated is reduced. Then, the colloidal silica contained in the chemical conversion treatment liquid of the main body is further gelled by bringing the chemical conversion treatment liquid of the main body into contact with the gelled colloidal silica. Therefore, in the reactive chemical conversion treatment liquid of the present embodiment, the thickness of the chemical conversion coating tends to increase as the treatment time increases. This is in contrast to a conventional reaction-type chemical conversion treatment liquid. Since the corrosion resistance of the anticorrosive member tends to be improved when the thickness of the chemical conversion coating is increased, the corrosion resistance can be controlled by adjusting the treatment time when the chemical conversion treatment liquid of the present embodiment is used.
The chemical conversion treatment temperature at the time of bringing the chemical conversion treatment liquid into contact with the member to be treated may be set within a range of 20 ℃ to 60 ℃. In the present embodiment, since the chemical conversion treatment liquid is less susceptible to the treatment temperature, if it is within the above range, a rust-proof member having good corrosion resistance can be stably produced. If the temperature of the chemical conversion treatment liquid is too low, the viscosity of the liquid may decrease, and the workload such as stirring may increase. When the temperature of the chemical conversion treatment liquid is too high, the amount of volatilization of water as the solvent may increase, and the workload (water injection, agitation) for stabilizing the composition and viscosity of the chemical conversion treatment liquid may increase. If the chemical conversion treatment temperature is in the range of 30 ℃ to 55 ℃, the reduction in workability of the chemical conversion treatment step can be suppressed, and if the chemical conversion treatment temperature is in the range of 35 ℃ to 50 ℃, the rust-proof member having good corrosion resistance can be produced while ensuring good workability of the chemical conversion treatment step in a stable manner.
After the contact between the chemical conversion treatment liquid and the member to be treated is completed, the chemical conversion treatment liquid remaining on the surface of the member to be treated is cleaned and removed, and dried. The cleaning method is not limited, but in general, a rinsing with accumulated water and a rinsing with running water subsequent thereto are performed. The drying conditions can be set appropriately. By increasing the drying temperature and the drying time, the stability of the chemical conversion coating can be expected to be improved. By way of non-limiting example, the drying temperature is preferably 40 ℃ or higher, more preferably 50 ℃ or higher, and particularly preferably 70 ℃ or higher. The drying time may be set according to the relationship with the drying temperature. By way of non-limiting example, the drying time may be set to 20 minutes when the drying temperature is 40 ℃, 10 minutes when the drying temperature is 50 ℃, or 5 minutes when the drying temperature is 70 ℃.
In the chemical conversion treatment, a substance constituting a chemical conversion coating film is formed by an increase in pH of the chemical conversion treatment liquid in the vicinity of the surface, which is generated when zinc dissolves from the surface of the member to be treated, and therefore a zinc-containing substance (such as zinc ions or zinc complex ions) is inevitably dissolved in the chemical conversion treatment liquid during use. The zinc-equivalent concentration of the zinc-containing substance may affect the process of dissolving zinc from the workpiece, and may affect the film thickness and film quality of the chemical conversion coating. However, in the chemical conversion treatment liquid of the present embodiment, as described above, in the high pH region, the colloidal silica gels and the fluidity of the chemical conversion treatment liquid decreases, and the mass transfer with the chemical conversion treatment liquid in the main region decreases. Therefore, the zinc-reduced concentration of the zinc-containing substance of the chemical conversion treatment liquid located in the high pH region is higher than the zinc-reduced concentration of the zinc-containing substance of the chemical conversion treatment liquid of the main body. Therefore, as a result, in the chemical conversion treatment liquid of the present embodiment, the zinc-equivalent concentration of the zinc-containing substance hardly affects the characteristics (film thickness, composition, and the like) of the chemical conversion coating film. That is, the chemical conversion treatment liquid of the present embodiment has high robustness against contamination with zinc.
Similarly, iron-containing substances (iron ions, iron complex ions, and the like) derived from the base material and the like are dissolved in the chemical conversion treatment liquid during use. The content of the iron-containing substance tends to increase with the increase of the use time. As described above, the chemical conversion treatment liquid according to the present embodiment is less susceptible to the composition of the chemical conversion treatment liquid as a main component in the region where the chemical conversion coating is formed near the surface of the member to be treated, and therefore has high robustness against iron contamination.
The embodiments described above are described to facilitate understanding of the present invention, and are not described to limit the present invention. Therefore, the elements disclosed in the above embodiments are intended to include all design modifications and equivalents that fall within the technical scope of the present invention. For example, the chemical conversion coating may contain an organic binder component. In this case, the chemical conversion treatment liquid may contain a component that provides an organic binder component, or a region in which an organic protective coating layer that can be positioned as the inorganic chemical conversion coating film is formed on the Si-rich region.
The present invention includes the following aspects.
(1) A chemical conversion treatment solution characterized by containing colloidal silica, a water-soluble substance containing trivalent chromium, and a water-soluble substance containing an organic acid having a high pKa, and having a pH of 3.0 or more.
(2) The chemical conversion treatment solution according to item (1) above, wherein the colloidal silica is contained in an amount of 2g/L to 25g/L inclusive, the trivalent chromium-containing water-soluble substance is contained in an amount of 1g/L to 6g/L inclusive in terms of trivalent chromium, and the high pKa organic acid-equivalent content of the high pKa organic acid-containing water-soluble substance is 0.2 to 2 inclusive in terms of a molar ratio to the trivalent chromium-equivalent content of the trivalent chromium-containing water-soluble substance.
(3) The chemical conversion treatment solution according to the above (1) or (2), wherein the high pKa organic acid contained in the water-soluble substance containing a high pKa organic acid comprises a hydroxymonocarboxylic acid.
(4) The chemical conversion treatment liquid according to any one of the above (1) to (3), further comprising a water-soluble substance containing a film-forming metal.
(5) The chemical conversion treatment solution according to any one of the above (1) to (4), wherein a ratio of a content (unit: g/L) of the colloidal silica to a content (unit: g/L) of the water-soluble substance containing the high-pKa organic acid in terms of the high-pKa organic acid (colloidal silica/high-pKa organic acid) is in a range of 0.5 to 10.
(6) The chemical conversion treatment solution according to any one of the above (1) to (5), further comprising a water-soluble substance containing a low pKa organic acid, wherein a molar ratio of a content of the low pKa organic acid-equivalent water-soluble substance containing a low pKa organic acid to a content of the high pKa organic acid-equivalent water-soluble substance containing a high pKa organic acid is 3 or less.
(7) The chemical conversion treatment liquid according to any one of the above (1) to (6), wherein the chemical conversion treatment liquid is of a reactive type.
(8) A method for manufacturing a rust-preventive member, characterized by comprising: a plating step of forming the zinc-based plating layer on the base material to obtain a member to be treated that includes the base material and the zinc-based plating layer; and a chemical conversion treatment step of bringing the member to be treated into contact with the chemical conversion treatment liquid described in (7) above, and then cleaning the member to be treated to form a chemical conversion coating on the member to be treated.
(9) The method for producing a rustproof member according to item (8) above, wherein the base material is a cast product.
Examples
The effects of the present invention will be described below based on examples, but the present invention is not limited thereto.
(examples 1 to 4)
A rust-preventive member was produced under the following conditions.
(1) Base material: an iron-based cast member (100 mm. Times.50 mm, thickness 8.0 mm).
(2) Zinc plating layer: electrogalvanizing ("FZ-77A 1 (primary brightener)/GC 1 (secondary brightener)" manufactured by lapping industries, ltd.) was carried out to form a plating film having a thickness of 10 μm.
(3) Chemical conversion treatment solution: the compositions shown in Table 1.
(4) Chemical conversion treatment: the sample was immersed in the chemical conversion treatment solution at 45 ℃ for 40 seconds while bubbling (air agitation) (example 1 only, further immersion was stopped for 30 seconds), washed with water (rinsing with running water after rinsing the stored water), and dried (80 ℃ C., 10 minutes).
[ Table 1]
In the preparation of the chemical conversion treatment solution, chromium chloride was used as a chromium source, titanium tetrachloride was used as a titanium source, aluminum chloride was used as an aluminum source, glycolic acid was used as a high pKa organic acid, and hydrochloric acid, sodium hydroxide, and potassium hydroxide were used to adjust the pH. As shown in table 1, the shine was not noticeable in any of the examples with respect to the treated appearance, and the appearance color was white to blue. The appearance can be adjusted by changing the content of the water-soluble substance containing a film-forming metal containing Ti or Al. Specifically, the treatment appearance can be bluish by increasing the content of the water-soluble substance containing a film-forming metal containing Ti and Al.
Supplying the rust-preventive member to JIS Z2371:2015, the time until white rust is produced (white rust production time) is measured by visual observation at predetermined intervals in a neutral salt spray test (SST: salt spray testing). Specifically, the surface of the rust preventive member was visually observed every 12 hours from the start of the test, and when white rust was observed in 1% or more of the measurement area, the test time for this observation was taken as the white rust generation time. The measurement results are shown in table 2. In comparative example 1, the same base material (galvanized iron-based cast member) as in example 1 was immersed in a normal reaction-type chemical conversion treatment liquid ("YFA-S/30 HR", manufactured by lapping industries, ltd.) for 40 seconds under standard conditions to obtain a rust-proof member.
[ Table 2]
| White rust development time (hours) | |
| Example 1 | 504 |
| Example 2 | 360 |
| Example 3 | 240 |
| Example 4 | 240 |
| Comparative example 1 | 96 |
(example 5)
The chemical conversion treatment liquid of example 1 was used to evaluate the robustness of the chemical conversion treatment.
Supplying the rust-preventive member to JIS Z2371: in the neutral salt spray test described in 2015, the rust-preventive member was visually observed after 480 hours of the test time, and evaluated according to the following criteria.
A: white rust was not observed in the measurement area.
B: the white rust generation area ratio in the measurement area was less than 5%.
C: the white rust generation area ratio in the measurement region is 5% or more.
Example 5-1 coating film thickness
The thickness of the electrogalvanized film is changed. The results are shown in Table 3.
[ Table 3]
| Coating thickness (mum) | Evaluation results |
| 5 | B |
| 10 | A |
| 20 | A |
| 30 | A |
Example 5-2 brightener concentration
The compounding of the brightener in the plating solution for forming electrogalvanizing is changed. The results are shown in Table 4. The column of "brightener ratio" in Table 4 indicates "the amount of primary brightener added (unit: mL/L)/the amount of secondary brightener added (unit: mL/L)".
[ Table 4]
| Brightener ratio | Evaluation results |
| 50/1 | B |
| 80/2 | A |
| 100/1 | A |
| 70/0.5 | A |
| 70/1.5 | A |
(example 5-3) chemical conversion treatment time
The treatment time of the chemical conversion treatment was changed. The results are shown in Table 5.
[ Table 5]
| Treatment time (seconds) | Evaluation results |
| 20 | B |
| 30 | B |
| 40 | A |
| 60 | A |
(example 5-4) chemical conversion treatment temperature
The treatment temperature of the chemical conversion treatment was changed. The results are shown in Table 6.
[ Table 6]
| Treatment temperature (. Degree.C.) | Evaluation results |
| 35 | A |
| 45 | A |
| 50 | A |
(example 5-5) pH of chemical conversion treatment solution
The pH of the chemical conversion treatment solution was changed. The results are shown in Table 7.
[ Table 7]
| pH | Evaluation results |
| 3.0 | B |
| 3.5 | A |
| 4.0 | A |
(examples 5 to 6) drying temperature
The drying temperature after the chemical conversion treatment was changed. The results are shown in Table 8.
[ Table 8]
| Drying temperature (. Degree.C.) | Evaluation results |
| 50 | B |
| 60 | B |
| 70 | A |
| 80 | A |
| 100 | A |
(examples 5 to 7) Zinc concentration of chemical conversion treatment solution
When preparing the chemical conversion treatment liquid, zinc chloride was added to change the zinc equivalent concentration of the zinc-containing substance in the chemical conversion treatment liquid. The results are shown in Table 9.
[ Table 9]
(examples 5 to 8) iron concentration of chemical conversion treatment solution
When the chemical conversion treatment liquid was prepared, ferric chloride was added to change the iron-equivalent concentration of the iron-containing substance in the chemical conversion treatment liquid. The results are shown in Table 10.
[ Table 10]
Example 6 composition of chemical conversion treatment liquid
Various chemical conversion treatment liquids (treatment liquid 4-1 to treatment liquid 4-36) were prepared by changing the contents of components other than colloidal silica (Cr, ti, al, high pKa organic acid) and the contents of colloidal silica as shown in table 11 based on the composition of example 4. The compositions of the treatment solutions 4 to 22 were the same as those of the chemical conversion treatment solution of example 4, and the pH of any of the treatment solutions was 3.3. The obtained rust-preventive member was subjected to SST by the same chemical conversion treatment as in example 4. The rust inhibitive member was visually observed at test times of 72 hours, 168 hours, and 264 hours to measure the white rust generation area ratio (unit:%). The results of measuring the white rust area ratio are shown in table 11.
[ Table 11]
| Treatment liquid | Other than silica | Silicon dioxide | 72h | 168h | 264h |
| 4-1 | 0.4 times of | 0.4 times of | 0 | 3 | 15 |
| 4-2 | 0.4 times of | 0.6 times of | 0 | 1 | 8 |
| 4-3 | 0.4 times of | 0.8 times of | 0 | 1 | 8 |
| 4-4 | 0.4 times of | 1 time of | 0 | 0 | 5 |
| 4-5 | 0.4 times of | 1.2 times of | 0 | 0 | 2 |
| 4-6 | 0.4 times of | 1.4 times of | 0 | 0 | 1 |
| 4-7 | 0.6 times of | 0.4 times of | 0 | 3 | 15 |
| 4-8 | 0.6 times of | 0.6 times of | 0 | 1 | 10 |
| 4-9 | 0.6 times of | 0.8 times of | 0 | 0 | 2 |
| 4-10 | 0.6 times of | 1 times of | 0 | 0 | 0 |
| 4-11 | 0.6 times of | 1.2 times of | 0 | 0 | 0 |
| 4-12 | 0.6 times of | 1.4 times of | 0 | 1 | 1 |
| 4-13 | 0.8 times of | 0.4 times of | 0 | 1 | 20 |
| 4-14 | 0.8 times of | 0.6 times of | 0 | 1 | 5 |
| 4-15 | 0.8 times of | 0.8 times of | 0 | 0 | 10 |
| 4-16 | 0.8 times of | 1 times of | 0 | 0 | 2 |
| 4-17 | 0.8 times of | 1.2 times of | 0 | 0 | 1 |
| 4-18 | 0.8 times of | 1.4 times of | 0 | 0 | 2 |
| 4-19 | 1 times of | 0.4 times of | 0 | 1 | 5 |
| 4-20 | 1 times of | 0.6 times of | 0 | 1 | 4 |
| 4-21 | 1 times of | 0.8 times of | 0 | 0 | 2 |
| 4-22 | 1 times of | 1 times of | 0 | 1 | 1 |
| 4-23 | 1 times of | 1.2 times of | 0 | 0 | 1 |
| 4-24 | 1 times of | 1.4 times of | 0 | 0 | 1 |
| 4-25 | 1.2 times of | 0.4 times of | 0 | 2 | 10 |
| 4-26 | 1.2 times of | 0.6 times of | 0 | 2 | 5 |
| 4-27 | 1.2 times of | 0.8 times of | 0 | 0 | 3 |
| 4-28 | 1.2 times of | 1 times of | 0 | 0 | 2 |
| 4-29 | 1.2 times of | 1.2 times of | 0 | 1 | 7 |
| 4-30 | 1.2 times of | 1.4 times of | 0 | 0 | 3 |
| 4-31 | 1.4 times of | 0.4 times of | 0 | 5 | 30 |
| 4-32 | 1.4 times of | 0.6 times of | 0 | 2 | 8 |
| 4-33 | 1.4 times of | 0.8 times of | 0 | 0 | 5 |
| 4-34 | 1.4 times of | 1 times of | 0 | 1 | 5 |
| 4-35 | 1.4 times of | 1.2 times of | 0 | 0 | 4 |
| 4-36 | 1.4 times of | 1.4 times of | 0 | 1 | 3 |
As shown in table 11, it was confirmed that: the rust-preventive member formed by using any of the treatment liquids had a white rust generation area ratio of 5% or less and had good corrosion resistance until the test time was 168 hours.
The results of the test for 264 hours are shown in matrix form (table 12). In table 12, a region having a white rust occurrence area ratio of 5% or less is surrounded by a thick line. In this region, only two white rust occurrence area ratios exceed 5% and are 10% or less. The results are shown in the boxes of the two-dot chain line in table 12.
[ Table 12]
It can be confirmed that: when the content of the colloidal silica is relatively large, a rust-proof coating film excellent in corrosion resistance can be stably obtained even if the content of the component other than the colloidal silica slightly varies.
(example 7) influence of organic acid species
As shown in Table 13, chemical conversion treatment liquids 4-37 to 4-40 were prepared by changing a part of the organic acid with a high pKa to oxalic acid (the lowest pKa was 1.27) which is one type of organic acid with a low pKa, with respect to the chemical conversion treatment liquid of example 4. In addition, the chemical conversion treatment liquid of comparative example 2 was prepared by changing all the high pKa organic acids in the chemical conversion treatment liquid of example 4 to oxalic acid. In the row of "organic acid molar ratio" in table 13, the molar ratio of the low pKa organic acid-converted content of the water-soluble substance containing a low pKa organic acid to the high pKa organic acid-converted content of the water-soluble substance containing a high pKa organic acid (low pKa organic acid/high pKa organic acid) is shown. As shown in table 13, the chemical conversion treatment liquids 4-37 to 4-40 were chemical conversion treatment liquids having organic acid molar ratios in the range of 0.1 to 3 different from those of example 4, compared with the chemical conversion treatment liquid of example 4.
[ Table 13]
These chemical conversion treatment liquids were used to produce rust-proof members. The obtained rust inhibitive member was subjected to the same test as in example 6. The results of measuring the white rust area ratio (unit:%) at each measurement time are shown in table 14.
[ Table 14]
| Treatment liquid | 72h | 168h | 264h |
| Example 4 | 0 | 1 | 1 |
| 4-37 | 0 | 0 | 1 |
| 4-38 | 0 | 1 | 3 |
| 4-39 | 0 | 1 | 5 |
| 4-40 | 1 | 3 | 10 |
| Comparative example 2 | 2 | 5 | 30 |
The rustproof member produced using the chemical conversion treatment liquid of comparative example 2 had an area ratio of white rust generation of 2% at 72 hours.
Claims (7)
1. A method for producing a rust-preventive member, characterized in that,
the method comprises a chemical conversion treatment step of bringing a chemical conversion treatment liquid into contact with a member to be treated containing zinc on the surface thereof, cleaning the member to be treated, and forming a chemical conversion coating on the member to be treated,
as for the chemical conversion treatment liquid,
comprises the following components: colloidal silicon dioxide; the trivalent chromium-containing water-soluble substance is an ionic substance containing trivalent chromium; and a water-soluble substance of an organic acid having a high pKa, which is an organic acid having a lowest pKa of 3.5 or more,
the chemical conversion treatment liquid has a pH of 3.0 or more and 4.5 or less in a state before being brought into contact with the member to be treated,
the high pKa organic acid comprises glycolic acid,
the chemical conversion treatment liquid is not limited to the case where it contains at least one selected from the group consisting of allylamine, polyallylamine, aromatic sulfonic acid-formaldehyde condensate, and derivatives thereof.
2. The method for manufacturing a rust inhibitive member according to claim 1,
in the chemical conversion treatment liquid,
the content of the colloidal silica is more than 2g/L and less than 25g/L,
the trivalent chromium content of the water-soluble material containing trivalent chromium is 1g/L to 6g/L,
the high-pKa organic acid-containing water-soluble substance has a high-pKa organic acid-equivalent content of 0.2 to 2 inclusive in terms of a molar ratio to the trivalent chromium-equivalent content of the trivalent chromium-containing water-soluble substance.
3. The method of manufacturing a rust inhibitive member according to claim 1 or 2,
the chemical conversion treatment liquid further contains a water-soluble substance containing a film-forming metal, and the water-soluble substance containing the film-forming metal is a water-soluble substance containing a metal ion capable of forming a film by interacting with oxygen.
4. The manufacturing method of a rust inhibitive member according to any one of claims 1 to 3,
in the chemical conversion treatment liquid, a ratio of a content of colloidal silica to a high pKa organic acid equivalent content of the water-soluble substance containing a high pKa organic acid, namely, colloidal silica/high pKa organic acid, is in a range of 0.5 to 10, wherein a unit of the content of colloidal silica is g/L, and a unit of the high pKa organic acid equivalent content is g/L.
5. The manufacturing method of a rust inhibitive member according to any one of claims 1 to 4,
the chemical conversion treatment liquid further contains a water-soluble substance containing a low-pKa organic acid, wherein the water-soluble substance contains a low-pKa organic acid that is an organic acid having a lowest pKa of 1.27 or more and less than 3.5, and the molar ratio of the low-pKa organic acid-equivalent content of the water-soluble substance containing a low-pKa organic acid to the high-pKa organic acid-equivalent content of the water-soluble substance containing a high-pKa organic acid is 1 or less.
6. The method of manufacturing a rust inhibitive member according to any one of claims 1 to 5,
the member to be treated is formed by forming a zinc-based plating layer on a base material.
7. The method of manufacturing a rust inhibitive member according to claim 6,
the base material is a casting product.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2020148790A JP6868313B1 (en) | 2020-09-04 | 2020-09-04 | Method for manufacturing reaction type chemical conversion treatment liquid and rust preventive member |
| JP2020-148790 | 2020-09-04 | ||
| PCT/JP2021/030556 WO2022050079A1 (en) | 2020-09-04 | 2021-08-20 | Method for producing rust-proof member |
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| CN115362284A true CN115362284A (en) | 2022-11-18 |
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| US (1) | US20230140575A1 (en) |
| EP (1) | EP4123051A4 (en) |
| JP (1) | JP6868313B1 (en) |
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| WO2022209019A1 (en) * | 2021-03-31 | 2022-10-06 | ユケン工業株式会社 | Chemical conversion treatment liquid, and method for manufacturing member in which chemical conversion film is provided on surface |
| CN115413300B (en) | 2021-03-31 | 2023-11-21 | 油研工业股份有限公司 | Chemical conversion treatment liquid and method for producing member having chemical conversion coating film on surface of member |
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2020
- 2020-09-04 JP JP2020148790A patent/JP6868313B1/en active Active
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2021
- 2021-08-20 CN CN202180026107.1A patent/CN115362284A/en active Pending
- 2021-08-20 US US17/995,177 patent/US20230140575A1/en not_active Abandoned
- 2021-08-20 WO PCT/JP2021/030556 patent/WO2022050079A1/en active Application Filing
- 2021-08-20 EP EP21864137.1A patent/EP4123051A4/en active Pending
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| JP2022043493A (en) | 2022-03-16 |
| WO2022050079A1 (en) | 2022-03-10 |
| EP4123051A4 (en) | 2023-10-25 |
| US20230140575A1 (en) | 2023-05-04 |
| JP6868313B1 (en) | 2021-05-12 |
| EP4123051A1 (en) | 2023-01-25 |
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