WO2012137677A1 - Composition pour un traitement chimique et procédé de fabrication d'un élément ayant un film de revêtement de conversion chimique formé à partir de ladite composition - Google Patents

Composition pour un traitement chimique et procédé de fabrication d'un élément ayant un film de revêtement de conversion chimique formé à partir de ladite composition Download PDF

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Publication number
WO2012137677A1
WO2012137677A1 PCT/JP2012/058532 JP2012058532W WO2012137677A1 WO 2012137677 A1 WO2012137677 A1 WO 2012137677A1 JP 2012058532 W JP2012058532 W JP 2012058532W WO 2012137677 A1 WO2012137677 A1 WO 2012137677A1
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Prior art keywords
chemical conversion
water
acid
soluble
chromium
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PCT/JP2012/058532
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English (en)
Japanese (ja)
Inventor
良規 平松
真理 浅野
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Yuken Industry Co Ltd
Yuken Kogyo Co Ltd
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Yuken Industry Co Ltd
Yuken Kogyo Co Ltd
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Priority to JP2012518652A priority Critical patent/JP5838415B2/ja
Publication of WO2012137677A1 publication Critical patent/WO2012137677A1/fr
Anticipated expiration legal-status Critical
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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
    • 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

Definitions

  • the present invention relates to a composition for chemical conversion treatment capable of forming a chemical conversion film in which elution of hexavalent chromium harmful to the natural environment is suppressed, and to a member having a chemical conversion film formed by the treatment.
  • the present invention relates to a composition for chemical conversion treatment, a liquid composition for preparing the composition, and a method for producing a member having a chemical conversion film formed from the composition.
  • RoHS Restriction of the Use of Certain, Hazardous, Substances, Insect, Electrical and Electronic Equipment, and ELV (End of Life, Vehicles) It has been required to regulate the use of substances (lead, mercury, cadmium, hexavalent chromium, etc.).
  • a chromate coating effective as a chemical conversion coating for corrosion protection of a member having a metal surface such as a galvanized member is a composition for chemical conversion treatment using a chromate containing hexavalent chromium (hereinafter, chemical conversion treatment).
  • the composition for the above is not called “chemical conversion treatment liquid”), but is formed by chemical conversion treatment liquid containing trivalent chromium.
  • a chemical conversion film obtained by a conventional chemical conversion treatment solution containing hexavalent chromium contains soluble hexavalent chromium in the film. For this reason, such a film is subject to regulation by the above-mentioned directive.
  • Patent Document 1 a metal part on which a chemical conversion film is formed is immersed in a reduction treatment solution of a predetermined concentration in a reduction treatment process of hexavalent chromium for a predetermined set time, and dried to reduce the amount of elution of hexavalent chromium.
  • the reducing agent preferably used in this means is L-ascorbic acid.
  • Patent Document 2 discloses a method of adding a reducing agent that reduces hexavalent chromium to trivalent chromium in the chemical conversion treatment solution.
  • the reducing agent preferably used in this means is sodium bisulfite, and the addition of the reducing agent is performed before and after the addition of the supporting salt.
  • a new hexavalent chromium elution suppressing means for the chemical conversion film particularly a chemical conversion film capable of suppressing elution of hexavalent chromium even when stored in a high temperature and high humidity environment. It aims at providing a chemical conversion treatment means.
  • the present inventor examined solving the above-mentioned problem by an approach different from the prior art. That is, in the conventional technology, a material having a function of suppressing elution of hexavalent chromium (hereinafter referred to as “a conventional chemical conversion solution”) (hereinafter referred to as “a conventional chemical conversion solution”) containing a trivalent chromium existing in the past.
  • a conventional chemical conversion solution a material having a function of suppressing elution of hexavalent chromium
  • a conventional chemical conversion solution hereinafter referred to as “a conventional chemical conversion solution” containing a trivalent chromium existing in the past.
  • the present inventors have solved the above problem with a new approach of suppressing elution of hexavalent chromium by reviewing the type of organic acid compound that is a basic component of the chemical conversion treatment liquid containing trivalent chromium. Aimed.
  • a water-soluble dicarboxylic acid compound typified by oxalic acid is generally used as the organic acid compound, but instead of the water-soluble dicarboxylic acid compound, water-soluble dicarboxylic acid compound is used. It has been found that by using a hydroxycarboxylic acid-based substance, elution of hexavalent chromium can be suppressed even when stored in a high-temperature and high-humidity environment.
  • the water-soluble hydroxycarboxylic acid-based substance is selected from the group consisting of hydroxycarboxylic acids, hydroxycarboxylic acid ions, hydroxycarboxylic acid salts, and coordination compounds containing hydroxycarboxylic acid and / or hydroxycarboxylic acid ions. It means one or two or more selected substances that are soluble in a chemical conversion treatment solution that is an aqueous composition.
  • an aqueous acidic composition comprising a water-soluble trivalent chromium-containing substance and a water-soluble hydroxycarboxylic acid-based substance, and is water-soluble trivalent chromium.
  • the molar molar concentration in terms of chromium with respect to the total composition of the contained substances is 0.05 mol / L or more, and the molar concentration in terms of hydroxycarboxylic acids of the water-soluble hydroxycarboxylic acid-based substance is relative to the molar equivalent of chromium in water-soluble trivalent chromium-containing substance
  • the composition is a water-soluble cobalt-containing substance having a concentration of 2 mmol / L or more and 50 mmol / L or less in terms of cobalt and / or pyrogallol having a conversion in the range of 0.05 g / L or less and 3.0 g / L or less in terms of pyrogallol relative to the total composition.
  • a compound may be contained.
  • the pH of the above composition can be stably used in a wide range of 2.0 or more and 4.0 or less.
  • the present invention provides, as another aspect, obtaining a member having a chemical conversion film on zinc-based plating by bringing the composition for chemical conversion treatment into contact with the member subjected to zinc-based plating.
  • a method for producing a member having a characteristic chemical conversion film is provided.
  • this invention is another one aspect
  • the hexavalent chromium elution amount from the chemical conversion film excellent in the corrosion resistance and external appearance obtained by the chemical conversion liquid is high temperature, high humidity. Even after exposure to the environment, it can be suppressed to a particularly low level.
  • the chemical conversion liquid which concerns on this invention has a wide pH range which can form a favorable chemical conversion film stably compared with the chemical conversion liquid concerning a prior art, it is excellent in productivity.
  • composition for chemical conversion treatment is an aqueous acidic composition comprising a water-soluble trivalent chromium-containing substance and a water-soluble hydroxycarboxylic acid-based substance.
  • water-soluble trivalent chromium-based molar concentration of the water-soluble trivalent chromium-containing material is 0.05 mol / L or more
  • water-soluble trivalent water-soluble tricarboxylic acid-based molar concentration of the water-soluble hydroxycarboxylic acid-based material is 0.4 or more and less than 2.5.
  • a chemical conversion film having excellent corrosion resistance is formed while elution of hexavalent chromium is suppressed.
  • the member subjected to the chemical conversion treatment is also referred to as a “processed member”. Since the treatment temperature depends on the concentration, pH, etc., it cannot be determined definitely. When the temperature is 20 ° C. or higher, it is preferable to perform the treatment for 10 seconds or longer, and when the temperature is 40 ° C. or higher, the contact for 5 to 50 seconds is particularly preferable.
  • a contact method is not specifically limited, What is necessary is just to immerse a to-be-processed member in the chemical conversion liquid which concerns on this embodiment, or to spray the chemical conversion liquid on a to-be-processed member.
  • the member is rinsed with water or the like, and further dried to form a chemical conversion film on the metal surface of the member to be processed.
  • the chemical conversion treatment liquid according to the present embodiment is a coating type (a system in which a coating liquid layer formed of components of the processing liquid is formed on a member to be processed and a coating film obtained by drying the coating liquid layer is used as a chemical conversion film).
  • the coating liquid layer remaining on the member is removed by rinsing, and the chemical conversion treatment liquid and the member to be treated are in contact with each other while the chemical conversion treatment liquid and the member to be treated are in contact
  • the chemical conversion treatment liquid according to the present embodiment contains at least one water-soluble trivalent chromium-containing substance.
  • the water-soluble trivalent chromium-containing substance is selected from the group consisting of trivalent chromium (Cr 3+ ) and a water-soluble substance containing the same.
  • An example of the water-soluble substance containing trivalent chromium is Cr [H 2 O] 6 3+ .
  • water-soluble trivalent chromium-containing substance in water as a material blended to contain the water-soluble trivalent chromium-containing substance in the chemical conversion liquid, that is, as a raw material of the water-soluble trivalent chromium-containing substance. It is preferable to use a water-soluble compound (hereinafter referred to as “water-soluble trivalent chromium compound”).
  • water-soluble trivalent chromium compounds include reduction of hexavalent chromium compounds such as chromic acid and dichromate in addition to trivalent chromium salts such as chromium chloride, chromium sulfate, chromium nitrate, chromium phosphate and chromium acetate. Examples thereof include compounds reduced to trivalent by an agent.
  • the water-soluble trivalent chromium compound may be composed of only one kind of compound, or may be composed of a plurality of kinds.
  • the chemical conversion liquid which concerns on this embodiment does not contain hexavalent chromium substantially.
  • the content of the water-soluble trivalent chromium compound is 0.05 mol / L or more, preferably 0.07 mol / L or more in terms of chromium, from the viewpoint of easy formation of the chemical conversion film.
  • content of this water-soluble trivalent chromium compound means content of the component melt
  • the upper limit of the content of the water-soluble trivalent chromium compound is not particularly limited. However, if excessively contained, there is a possibility of causing a problem from the viewpoint of economy or waste liquid treatment, so the upper limit is about 0.5 mol / L. It is preferable to do. From the viewpoint of stably suppressing the hexavalent chromium elution amount, it is more preferably 0.25 mol / L or less.
  • the chemical conversion treatment liquid according to this embodiment contains a water-soluble hydroxycarboxylic acid-based material.
  • the “water-soluble hydroxycarboxylic acid-based substance” means a hydroxycarboxylic acid, a hydroxycarboxylic acid ion, a hydroxycarboxylic acid salt, and a hydroxycarboxylic acid and / or hydroxycarboxylic acid having at least one hydroxyl group in the molecule. It means one or two or more substances selected from the group consisting of coordination compounds containing carboxylic acid ions, which are compounds that are soluble in a chemical conversion treatment solution that is an aqueous composition. Therefore, it is not necessary for all of them to be dissolved in the chemical conversion solution, and a part of them may be dispersed or precipitated in the chemical conversion solution.
  • the chemical conversion film obtained from the chemical conversion treatment liquid according to the present embodiment contains a water-soluble dicarboxylic acid compound (in this embodiment, “dicarboxylic acid” is a carboxylic acid) because the chemical conversion treatment liquid contains a water-soluble hydroxycarboxylic compound.
  • a water-soluble dicarboxylic acid compound in this embodiment, “dicarboxylic acid” is a carboxylic acid
  • dicarboxylic acid compound means dicarboxylic acid, dicarboxylic acid ion, dicarboxylic acid salt and dicarboxylic acid and / or dicarboxylic acid ion based on this definition.
  • the chemical conversion treatment liquid according to the present embodiment can form a chemical conversion film having particularly excellent temporal stability by using a water-soluble hydroxycarboxylic acid-based substance as a basic component instead of the water-soluble dicarboxylic acid compound. It is.
  • Hydroxycarboxylic acids can be broadly classified into aliphatic hydroxycarboxylic acids and aromatic hydroxycarboxylic acids.
  • aliphatic hydroxycarboxylic acids include glycolic acid, lactic acid, ⁇ -hydroxypropionic acid, tartronic acid, glyceric acid, 2-hydroxybutyric acid, 3-hydroxybutyric acid, ⁇ -hydroxybutyric acid, malic acid, tartaric acid, citramalic acid,
  • Examples include citric acid, isocitric acid, leucine acid, mevalonic acid, pantoic acid, ricinoleic acid, ricinaleic acid, cerebric acid, quinic acid and shikimic acid.
  • aromatic hydroxy acids examples include monohydroxybenzoic acid derivatives such as salicylic acid, creosote acid, vanillic acid, and syringic acid; dihydroxybenzoic acid derivatives such as pyrocatechuic acid, resorcylic acid, protocatechuic acid, gentisic acid, and orthoric acid; gallic acid Trihydroxybenzoic acid derivatives such as acids; phenylacetic acid derivatives such as atrolactic acid, benzylic acid and mandelic acid; cinnamic acids such as melirotoic acid, furoretic acid, coumaric acid, umberic acid, caffeic acid, ferulic acid and sinapinic acid And acid derivatives.
  • monohydroxybenzoic acid derivatives such as salicylic acid, creosote acid, vanillic acid, and syringic acid
  • dihydroxybenzoic acid derivatives such as pyrocatechuic acid, resorcylic acid, protocatechuic acid,
  • the hydroxycarboxylic acid according to the present embodiment is preferably an aliphatic hydroxycarboxylic acid from the viewpoint of the solubility in the chemical conversion treatment liquid according to the present embodiment, which is an aqueous composition, and the difficulty of generating by-products.
  • the number is preferably small.
  • the ratio of the number of carboxylic acid groups (including the case of ionization) in the molecule to the number of hydroxyl groups (number of carboxylic acid groups / number of hydroxyl groups) is preferably close to 1, and this ratio is 1, that is, It is particularly preferable that the number of carboxylic acid groups is equal to the number of hydroxyl groups.
  • particularly preferable compounds as the hydroxycarboxylic acid according to the present embodiment are aliphatic monohydroxymonocarboxylic acids having 4 or less carbon atoms such as glycolic acid, hydroxypropionic acid, and hydroxybutyric acid.
  • the kind of metal ion which comprises hydroxycarboxylate is not specifically limited.
  • the specific structure of the coordination compound of hydroxycarboxylic acid is not particularly limited. Any substance may be dissolved in the chemical conversion liquid which is an aqueous composition.
  • the molar concentration in terms of hydroxycarboxylic acid of the water-soluble hydroxycarboxylic acid-based material according to the present embodiment is 0 as a ratio (hereinafter also referred to as “HC / Cr ratio”) to the molar concentration in terms of chromium of the water-soluble trivalent chromium-containing material. 4 to less than 2.5.
  • the molar concentration of water-soluble hydroxycarboxylic acid-based substance in terms of hydroxycarboxylic acid is the hydroxycarboxylic acid equivalent of the component dissolved in the chemical conversion treatment liquid among the water-soluble hydroxycarboxylic acid-type substances present in the chemical conversion treatment liquid. Mean molar concentration.
  • the HC / Cr ratio is preferably in the range of 0.8 to 2.2.
  • the water-soluble hydroxycarboxylic acid-based material according to the present embodiment may be added as a hydroxycarboxylic acid, or may be added as a hydroxycarboxylic acid salt or a coordination compound in preparing the chemical conversion treatment liquid. Alternatively, it may be added as a lactone or a derivative such as an ester.
  • Optional addition component (A) Water-soluble cobalt-containing substance
  • the chemical conversion treatment liquid according to this embodiment may contain a cobalt-containing substance.
  • the water-soluble cobalt-containing material is selected from the group consisting of cobalt ions (Co 2+ ) and water-soluble materials containing the same. Examples of water-soluble cobalt-containing substances include Co [H 2 O] 6 2+ , coordination compounds of cobalt ions and carboxylic acid compounds, and the like.
  • a water-soluble compound capable of producing a water-soluble cobalt-containing substance in water (hereinafter referred to as “a water-soluble cobalt-containing substance”) as a raw material for the water-soluble cobalt-containing substance, It is preferable to use "water-soluble cobalt compound”).
  • water-soluble cobalt compounds examples include cobalt chloride, cobalt sulfate, cobalt nitrate, cobalt phosphate, and cobalt acetate.
  • the water-soluble cobalt compound may be composed of only one kind of compound, or may be composed of a plurality of kinds.
  • the content of the water-soluble cobalt-containing substance is preferably 50 mmol / L or less in terms of cobalt.
  • content of this water-soluble cobalt compound means content of the component melt
  • the content exceeds 50 mmol / L, the effect of increasing the elution amount of hexavalent chromium may be superior to the effect of improving the corrosion resistance.
  • it since it may show the tendency for corrosion resistance to fall rather when it contains a water-soluble cobalt containing substance excessively, it shall be 20 mmol / L or less in cobalt conversion from a viewpoint of ensuring the effect which improves corrosion resistance stably. In this range, it is particularly preferable to set the content to a minimum that can achieve the purpose of ensuring the corrosion resistance determined by the application.
  • the content of the water-soluble cobalt-containing substance may be in the range of 4 mmol / L or more and 20 mmol / L or less in terms of cobalt, and a salt spray test in accordance with JIS Z2371 is performed for 72 hours. Even after performing, it is achieved that the white rust area ratio in the obtained chemical conversion film is 5% or less of the whole.
  • the chemical conversion treatment liquid according to the present embodiment may contain a pyrogallol compound in order to further suppress the elution of hexavalent chromium from the chemical conversion film obtained by the chemical conversion treatment liquid.
  • the “pyrogallol compound” means one or more compounds selected from pyrogallol and alkylpyrogallol having 3 or less carbon atoms.
  • Alkyl pyrogallols such as 5-methyl pyrogallol and 5-ethyl pyrogallol also exhibit performance equivalent to that of pyrogallol as long as the alkyl group has 3 or less carbon atoms.
  • the concentration of the pyrogallol compound in the chemical conversion solution is not particularly limited, but is preferably 0.05 g / L or more and 3.0 g / L or less.
  • the concentration of the pyrogallol compound in the chemical conversion treatment liquid means the content of a component dissolved in the chemical conversion treatment liquid out of the concentration of the pyrogallol compound present in the chemical conversion treatment liquid.
  • the concentration of the pyrogallol compound is excessively low, the effect of addition cannot be obtained.
  • it is excessively high the appearance of the treatment becomes darker than yellow and becomes brownish, and an undissolved component is easily generated in the concentrated liquid described later.
  • the chemical conversion treatment liquid according to this embodiment is selected from the group consisting of metal ions, inorganic acids and their anions, inorganic colloids, silane coupling agents, organophosphorus compounds, and fluorine compounds in addition to the above substances.
  • metal ions inorganic acids and their anions
  • inorganic colloids silane coupling agents
  • organophosphorus compounds organophosphorus compounds
  • fluorine compounds fluorine compounds in addition to the above substances.
  • One or two or more selected may be included.
  • a kind selected from the group consisting of polymers such as waxes, corrosion inhibitors, surfactants such as diols, triols, amines, plastic dispersions, dye generators such as dyes, pigments and metal dye generators, desiccants and dispersants Or you may contain the 2 or more types of material further.
  • metal ions examples include Al, Si, Ni, Na, K, Ag, Fe, Ca, Mg, Zr, Sc, Ti, Mn, Cu, Zn, Sn, Mo, V, and W ions. It may be present in the form of oxyacid ions such as ions.
  • Inorganic acids include hydrohalic acid such as hydrochloric acid, hydrofluoric acid, hydrobromic acid, chloric acid, perchloric acid, chlorous acid, hypochlorous acid, sulfuric acid, sulfurous acid, nitric acid, nitrous acid,
  • hydrohalic acid such as hydrochloric acid, hydrofluoric acid, hydrobromic acid, chloric acid, perchloric acid, chlorous acid, hypochlorous acid, sulfuric acid, sulfurous acid, nitric acid, nitrous acid
  • phosphoric acid orthophosphoric acid
  • polyphosphoric acid metaphosphoric acid
  • pyrophosphoric acid pyrophosphoric acid
  • ultraphosphoric acid hypophosphorous acid
  • superphosphoric acid especially from hydrohalic acid, sulfuric acid, nitric acid and phosphoric acid (orthophosphoric acid) It is preferable that 1 type, or 2 or more types chosen from the group which consists of is comprised as an anion.
  • the concentration of these acids and / or acid ions in the chemical conversion solution is not particularly limited.
  • the ratio of the total molar concentration of acid in terms of acid to the total molar concentration of trivalent chromium and the above metal ions is 0.1 to 10, and preferably 0.5 to 3.
  • examples of the inorganic colloid include silica sol, alumina sol, titanium sol, and zirconia sol, and examples of the silane coupling agent include vinyltriethoxysilane and ⁇ -methacryloxypropyltrimethoxysilane.
  • organic phosphonic acid compound means a compound composed of one or more selected from the group consisting of organic phosphonic acid, organic phosphonic acid ions, and organic phosphonates.
  • R—P ( ⁇ O) (OH) 2 R is an organic group
  • organic phosphonic acids 1-hydroxyethylidene-1,1-diphosphonic acid, 2-phosphonobutane 1,2,4-tricarboxylic acid, amino (trimethylenephosphonic acid), ethylenediaminetetra (methylenephosphonic acid) and diethylenetriaminepenta (methylenephosphonic) Acid).
  • salts of these organic phosphonic acids 1-hydroxyethylidene-1,1-diphosphonic acid tetrasodium salt, 1-hydroxyethylidene-1,1-diphosphonic acid trisodium salt, ethylenediaminetetra (methylenephosphonic acid) pentasodium salt, Examples include diethylenetriaminepenta (methylenephosphonic acid) 7 sodium salt. In these salts, sodium ions are often dissociated in the chemical conversion solution.
  • the chemical conversion treatment liquid according to the present embodiment contains a water-soluble hydroxycarboxylic acid-based substance instead of the water-soluble dicarboxylic acid compound that is generally contained in the conventional chemical conversion treatment liquid as one of the basic components, It is preferable not to contain a water-soluble organic acid compound other than the water-soluble hydroxycarboxylic acid compound.
  • a water-soluble organic acid compound other than the water-soluble hydroxycarboxylic acid substance may be contained as long as the elution amount of hexavalent chromium is not significantly increased.
  • the chemical conversion liquid which concerns on this embodiment does not contain organic film-forming components, such as an organic resin material and its precursor (a monomer, an oligomer, etc.) substantially.
  • organic film-forming components such as an organic resin material and its precursor (a monomer, an oligomer, etc.) substantially.
  • “substantially” means that a very small amount of the corresponding component is inevitably mixed.
  • the chemical conversion treatment liquid according to the present embodiment does not substantially contain a fluorine-based substance such as a hexafluoro ion of a metal such as titanium or aluminum in consideration of the environment.
  • the chemical conversion liquid which concerns on this embodiment forms a chemical conversion film with few amounts of hexavalent chromium to elute, it does not contain a water-soluble hexavalent chromium containing substance substantially.
  • the solvent of the chemical conversion treatment liquid according to the present embodiment contains water as a main component.
  • a solvent other than water an organic solvent having high solubility in water, such as alcohol, ether, and ketone, may be mixed.
  • the ratio shall be 10 volume% or less with respect to all the solvents from a viewpoint of stability of the whole chemical conversion liquid.
  • the chemical conversion treatment solution is made acidic from the viewpoint of proceeding with the chemical conversion treatment, and therefore the pH is less than 7.
  • the chemical conversion treatment liquid according to the present embodiment contains a water-soluble hydroxycarboxylic acid-based material instead of the water-soluble dicarboxylic acid compound, compared to the conventional chemical conversion treatment liquid containing the water-soluble dicarboxylic acid compound.
  • Wide pH range that can stably provide a chemical conversion film having excellent appearance and corrosion resistance.
  • the practical pH control range in the conventional chemical conversion treatment liquid is less than 1.0, but the chemical conversion treatment liquid according to the present embodiment is from 2 to 4 and specifically 2.0 or more. It is possible to stably provide a chemical conversion film having excellent characteristics over a wide range of 4.0 or less.
  • the composition according to this embodiment is a composition particularly suitable for forming a chemical conversion film on a zinc plating obtained by a chloride bath by adjusting the pH to 2.5 or more and 3.5 or less.
  • the composition is particularly suitable for forming a chemical conversion film on the zinc plating obtained by the zincate bath.
  • Concentrated composition for preparing a chemical conversion liquid A composition having fluidity having a composition in which the main components of the chemical conversion liquid are concentrated about 5 to 20 times (hereinafter referred to as “concentrated liquid for chemical conversion”). ) Is preferable because it saves the trouble of individually preparing the content of each component and facilitates storage.
  • the upper limit is set for the content in consideration of the solubility of each of the above components.
  • a water-soluble trivalent chromium-containing material and a water-soluble hydroxycarboxylic acid-based material are provided, and the molar molar concentration in terms of chromium with respect to the total composition of the water-soluble trivalent chromium-containing material is 0.25 mol / L or more.
  • the hexavalent chromium concentration per unit surface area of the chemical conversion film obtained from the chemical conversion liquid according to this embodiment is diphenylcarbazide described in EN (European Norm) 15205: 2006. Obtained by the following analysis method based on the colorimetric method.
  • the test member is cut so that the surface of the chemical conversion film is 50 ⁇ 5 cm 2 , and the cut member is put into a beaker.
  • the member after cutting is not heated in advance and is kept at room temperature. Put 55 mL of water that has been reduced to less than 1 ⁇ S / cm by passing through an ion exchange column, distillation, etc. into this beaker, add no zeolite, heat the beaker opening covered with a film, and boil for 10 minutes . After boiling, the beaker is air-cooled to room temperature, and the member is taken out to a constant volume of 50 mL.
  • a standard solution in which 0.113 g of potassium chromate was dissolved in 1000 mL of water was prepared, and 1 mL of each of the above 75% orthophosphoric acid and diphenylcarbazide solution was added thereto, and allowed to stand for 10 minutes. Measure.
  • the hexavalent chromium concentration of the test solution is calculated based on the absorbance of the standard solution, and the hexavalent chromium concentration per unit area of the test member is obtained from the result.
  • the chemical conversion film to be subjected to the above analysis is exposed to a high-temperature and high-humidity environment for a predetermined period, and analysis is performed after hexavalent chromium is easily eluted from the chemical conversion film.
  • the exposure to the high temperature and high humidity environment is stored for 72 hours in a constant temperature bath maintained at 80 ° C. and 90% RH for each member on which the chemical conversion film is formed.
  • products containing components with chemical conversion coatings may be placed in high-temperature and high-humidity environments in Southeast Asia and the like, so exposure to such high-temperature and high-humidity environments is not only an accelerated test, It also has a reproduction aspect.
  • the hexavalent chromium concentration per unit surface area in a chemical conversion film obtained by performing treatment with a conventional chemical conversion treatment solution is typically about 0.025 ⁇ g / cm 2 or more as a result of performing the above-described pretreatment and analysis method. Therefore, by the chemical conversion treatment using the chemical conversion treatment liquid according to the present embodiment, it is possible to realize an elution amount of 30% or less as compared with a normal chemical conversion coating.
  • the material of the member is not particularly limited as long as it is a member having a metal surface capable of forming this chromate film.
  • a preferable material for the member to be processed is a metal, and particularly a steel plate on which zinc-based plating is applied is particularly preferable.
  • the composition of the zinc-based plating may be pure zinc or, for example, a zinc alloy containing aluminum.
  • the plating method may be electroplating or hot dipping.
  • electroplating any of a cyan bath, a chloride bath, a sulfuric acid bath and a zincate bath may be used.
  • hot dipping alloying treatment may be performed after plating.
  • the chemical conversion treatment liquid according to the present embodiment can stably provide a chemical conversion film excellent in corrosion resistance and appearance regardless of the type of galvanization by electroplating. Specifically, even if the surface of the base material to be subjected to chemical conversion treatment is galvanized formed by either a chloride bath or a zincate bath, it is excellent in corrosion resistance and appearance, and hexavalent chromium elution is suppressed over a long period of time.
  • a chemical conversion film can be formed. It is preferable that the chemical conversion film formed from the chemical conversion liquid which concerns on this embodiment does not contain the metal salt of inorganic oxygen acid containing phosphorus, such as phosphoric acid. That is, it is preferable that the chemical conversion liquid which concerns on this embodiment does not contain the component based on the inorganic type oxygen acid containing phosphorus as a film-forming component.
  • Example 1 (1) Preparation of test member First, chromium nitrate as a water-soluble trivalent chromium compound is 0.76 mol / L in terms of chromium, and cobalt (II) hexahydrate as a water-soluble cobalt compound is 57 g / L.
  • a concentrated liquid for chemical conversion treatment containing 1 g / L of pyrogallol, 100 g / L of sodium nitrate and 1.0 mol / L of the organic acid of the type shown in Table 1 was prepared.
  • a chemical conversion treatment solution containing 100 mL / L of this concentrated solution and having a pH of 3.2 was prepared using nitric acid and sodium hydroxide.
  • the steel sheet (5 cm ⁇ 5 cm ⁇ t1 mm, surface area 50 cm 2 ) subjected to electrogalvanization (zincate bath) was washed with water according to a conventional method, and then immersed in nitric acid (67.5% nitric acid 3 ml / L, liquid temperature was room temperature) The surface was activated by performing an immersion time of 10 seconds.
  • the test member was further washed with water at room temperature for 10 seconds, and then immersed in the above chemical conversion solution (pH is 3.2) maintained at 30 ° C. and stirred for 30 seconds.
  • the test member pulled up from the treatment liquid was washed with water (normal temperature, 10 seconds) and then dried at 80 ⁇ 10 ° C. for 10 minutes.
  • Evaluation results Table 1 shows the evaluation results. Note that “-” in the table means that the evaluation cannot be performed or need not be performed because the properties of the chemical conversion solution are poor or the quality of the chemical conversion film is poor. is doing.
  • Chromium nitrate as water-soluble trivalent chromium compound is 0.76 mol / L in terms of chromium
  • cobalt nitrate (II) hexahydrate as water-soluble cobalt compound is 57 g / L
  • pyrogallol is 1 g / L
  • sodium nitrate is A concentrated liquid for chemical conversion treatment containing 100 g / L and 1.0 mol / L of the organic acid of the type shown in Table 2 was prepared.
  • a chemical conversion treatment solution containing 100 mL / L of this concentrated solution and having a pH of 3.2 was prepared using nitric acid and sodium hydroxide.
  • a steel plate (5 cm ⁇ 5 cm ⁇ t1 mm, surface area 50 cm 2 ) subjected to electrogalvanization (zincate bath) according to a conventional method was washed with water, and then immersed in nitric acid (67.5% nitric acid 3 ml / L, liquid temperature was room temperature, soaking time) The surface was activated by performing (for 10 seconds).
  • the test member was further washed with water at room temperature for 10 seconds, and then immersed in the above chemical conversion solution (pH is 3.2) maintained at 30 ° C. and stirred for 30 seconds.
  • the test member pulled up from the treatment liquid was washed with water (normal temperature, 10 seconds) and then dried at 80 ⁇ 10 ° C. for 10 minutes. Evaluation similar to Example 1 was performed with respect to the obtained test member. The evaluation results are shown in Table 2.
  • Chromium nitrate as water-soluble trivalent chromium compound is 0.76 mol / L in terms of chromium
  • cobalt nitrate (II) hexahydrate as water-soluble cobalt compound is 57 g / L
  • pyrogallol is 1 g / L
  • sodium nitrate is A concentrated solution for a chemical conversion treatment solution containing 100 g / L and lactic acid at concentrations shown in Table 3 was prepared.
  • a chemical conversion treatment solution containing 100 mL / L of this concentrated solution and having a pH of 3.2 was prepared using nitric acid and sodium hydroxide.
  • a steel plate (5 cm ⁇ 5 cm ⁇ t1 mm, surface area 50 cm 2 ) subjected to electrogalvanization (zincate bath) according to a conventional method was washed with water, and then immersed in nitric acid (67.5% nitric acid 3 ml / L, liquid temperature was room temperature, soaking time) The surface was activated by performing (for 10 seconds).
  • the test member was further washed with water at room temperature for 10 seconds, and then immersed in the above chemical conversion solution (pH is 3.2) maintained at 30 ° C. and stirred for 30 seconds.
  • the test member pulled up from the treatment liquid was washed with water (normal temperature, 10 seconds) and then dried at 80 ⁇ 10 ° C. for 10 minutes. Evaluation similar to Example 1 was performed with respect to the obtained test member. However, the test time of the salt spray test was 72 hours. The evaluation results are shown in Table 3.
  • Chromium nitrate as a water-soluble trivalent chromium compound is 0.76 mol / L in terms of chromium
  • cobalt nitrate (II) hexahydrate as a water-soluble cobalt compound is 57 g / L
  • sodium nitrate is 100 g / L.
  • a concentrated solution for a chemical conversion treatment solution containing an organic acid and, if necessary, pyrogallol was prepared.
  • a chemical conversion treatment solution containing 100 mL / L of this concentrated solution and having a pH of 3.2 was prepared using nitric acid and sodium hydroxide.
  • a steel plate (5 cm ⁇ 5 cm ⁇ t1 mm, surface area 50 cm 2 ) subjected to electrogalvanization (zincate bath) according to a conventional method was washed with water, and then immersed in nitric acid (67.5% nitric acid 3 ml / L, liquid temperature was room temperature, soaking time) The surface was activated by performing (for 10 seconds).
  • the test member was further washed with water at room temperature for 10 seconds, and then immersed in the above chemical conversion solution (pH is 3.2) maintained at 30 ° C. and stirred for 30 seconds.
  • the test member pulled up from the treatment liquid was washed with water (normal temperature, 10 seconds) and then dried at 80 ⁇ 10 ° C. for 10 minutes. Evaluation similar to Example 1 was performed with respect to the obtained test member. However, the test time of the salt spray test was 72 hours. The evaluation results are shown in Table 4.
  • chromium nitrate is 0.76 mol / L in terms of chromium
  • cobalt nitrate (II) hexahydrate as a water-soluble cobalt compound is the amount shown in Table 5 in terms of cobalt, and pyrogallol.
  • a concentrated solution for chemical conversion solution containing 1 g / L, 100 g / L of sodium nitrate and 1.0 mol / L of lactic acid was prepared.
  • a chemical conversion treatment solution containing 100 mL / L of this concentrated solution and having a pH of 3.2 was prepared using nitric acid and sodium hydroxide.
  • a steel plate (5 cm ⁇ 5 cm ⁇ t1 mm, surface area 50 cm 2 ) subjected to electrogalvanization (zincate bath) according to a conventional method was washed with water, and then immersed in nitric acid (67.5% nitric acid 3 ml / L, liquid temperature was room temperature, soaking time) The surface was activated by performing (for 10 seconds).
  • the test member was further washed with water at room temperature for 10 seconds, and then immersed in the above chemical conversion solution (pH is 3.2) maintained at 30 ° C. and stirred for 30 seconds.
  • the test member pulled up from the treatment liquid was washed with water (normal temperature, 10 seconds) and then dried at 80 ⁇ 10 ° C. for 10 minutes. Evaluation similar to Example 1 was performed with respect to the obtained test member. However, the test time of the salt spray test was 72 hours. The evaluation results are shown in Table 5.

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)
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Abstract

L'invention concerne un liquide pour un traitement chimique apte à former un film de revêtement de conversion chimique qui est excellent en termes de résistance à la corrosion et d'aspect et qui est empêché de libérer du chrome hexavalent. Ce liquide pour un traitement chimique est une composition acide à base aqueuse qui contient une substance contenant du chrome trivalent soluble dans l'eau, la quantité de la substance étant de 0,05 mol/L ou plus en termes de quantité de chrome par rapport à la composition totale, et une ou plusieurs substances acides hydrocarboxyliques solubles dans l'eau, choisies dans le groupe consistant en les acides hydroxycarboxyliques et les ions, sels et composés de coordination de ceux-ci, le rapport de la concentration molaire des substances acides hydroxycarboxyliques solubles dans l'eau en termes de la concentration du ou des acides hydroxycarboxyliques à la concentration molaire de la substance contenant du chrome trivalent, soluble dans l'eau, en termes de concentration de chrome étant de 0,4 ou plus mais inférieure à 2,5.
PCT/JP2012/058532 2011-04-01 2012-03-30 Composition pour un traitement chimique et procédé de fabrication d'un élément ayant un film de revêtement de conversion chimique formé à partir de ladite composition Ceased WO2012137677A1 (fr)

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JP2014159627A (ja) * 2013-01-24 2014-09-04 Yuken Industry Co Ltd 反応型化成処理用酸性組成物および化成皮膜をその表面に備える部材の製造方法
JP7133889B1 (ja) * 2021-03-31 2022-09-09 ユケン工業株式会社 化成処理液および化成皮膜をその表面に備える部材の製造方法
WO2022209019A1 (fr) * 2021-03-31 2022-10-06 ユケン工業株式会社 Liquide de traitement de conversion chimique et procédé de fabrication d'un élément dans lequel un film de conversion chimique est disposé sur la surface
EP3178947B1 (fr) * 2014-08-04 2022-11-02 Citizen Watch Co., Ltd. Cuir ou article en cuir et son procédé de production, agent de traitement du chrome hexavalent, procédé de traitement du chrome hexavalent dans le cuir brut ou un article en cuir brut

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JP7133889B1 (ja) * 2021-03-31 2022-09-09 ユケン工業株式会社 化成処理液および化成皮膜をその表面に備える部材の製造方法
WO2022209019A1 (fr) * 2021-03-31 2022-10-06 ユケン工業株式会社 Liquide de traitement de conversion chimique et procédé de fabrication d'un élément dans lequel un film de conversion chimique est disposé sur la surface
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