JP6216936B2 - Method for producing member having reactive composition and acidic coating for chemical conversion treatment and chemical coating on its surface - Google Patents

Description

  The present invention relates to a composition for chemical conversion treatment that can form a chemical conversion film that is substantially free of water-soluble cobalt-containing substances, has excellent corrosion resistance and is environmentally friendly, and a composition thereof. The manufacturing method of the member which equips the surface with the chemical conversion film formed by this.

  In recent years, environmental regulations such as RoHS (Restriction of the Use of Certain Hazardous Substances in Electrical and Electronic Equipment) Directive and ELV (End of Life Vehicles) Directive have been introduced. It has been required to regulate the use of substances (lead, mercury, cadmium, hexavalent chromium, etc.).

  In response to this trend, 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.

  In the chemical conversion treatment liquid containing trivalent chromium, in order to improve corrosion resistance, a water-soluble cobalt-containing substance may be contained (for example, Patent Document 1).

JP 2010-196174 A

  Cobalt, which is a metal related to a water-soluble cobalt-containing substance, is a kind of so-called rare metal and may be difficult to obtain stably at low cost. In addition, some of the cobalt-containing compounds with high availability (cobalt chloride, cobalt carbonate, cobalt nitrate and cobalt sulfate) belong to SVHC (Substance of Very High Concern). There are moves to limit the use of these substances in companies. For this reason, the chemical conversion treatment liquid containing trivalent chromium may be required to contain substantially no water-soluble cobalt-containing substance.

  In addition, regarding a chemical conversion film formed from a chemical conversion treatment solution, excessive dissolution of a metal component contained in the film during use may cause the metal component to adversely affect the environment. Unless denied, it is not preferable. Therefore, even if a certain chemical conversion film is excellent in corrosion resistance, if the excellent corrosion resistance is brought about by excessive elution of the metal component from the chemical conversion film, considering the influence on the environment, the metal component It may not be appropriate to include a water-soluble metal-containing substance that provides the chemical conversion treatment solution.

  In view of the present situation, the present invention contains a chemical conversion containing trivalent chromium that is substantially free of a water-soluble cobalt-containing substance, has excellent corrosion resistance, and can form a chemical conversion film with consideration for environmental conservation. It aims at providing a processing liquid. Another object of the present invention is to provide a method for producing a member provided on the surface thereof with a chemical conversion film formed by such a chemical conversion treatment liquid.

  As a result of studies conducted by the present inventors in order to solve the above problems, the following knowledge was obtained. In other words, in the chemical conversion treatment liquid containing trivalent chromium, a water-soluble titanium-containing substance is contained instead of a water-soluble cobalt-containing substance, and a carboxylic acid compound is also included, thereby providing excellent corrosion resistance and dissolution of metals. A chemical conversion film with a reduced amount can be formed.

The present invention completed based on the above findings is as follows.
(1) An acidic composition for reactive chemical conversion treatment that does not contain a water-soluble cobalt-containing substance, and 0.02 mol / L or more and 0.1 mol / L or less of a water-soluble trivalent chromium-containing substance in terms of chromium; Containing 0.0001 mol / L or more and 1 mol / L or less of a water-soluble titanium-containing substance in terms of titanium, and 0.001 mol / L or more and 0.2 mol / L or less of a carboxylic acid compound in terms of carboxylic acid, Contains one or more selected from the group consisting of citric acid compounds and oxalic acid compounds, and the citric acid equivalent content (unit: mol / L) of the citric acid compound in the acidic composition The first ratio, which is the ratio of the water-soluble trivalent chromium-containing substance to the chromium equivalent content (unit: mol / L), is 0.05 or more and 0.8 or less, and / or the acid The second ratio, which is the ratio of the oxalic acid equivalent content (unit: mol / L) of the oxalic acid compound to the chromium equivalent content (unit: mol / L) of the water-soluble trivalent chromium-containing substance in the composition. Ru der 0.05 to 2, reactive chemical conversion treatment for acidic composition.

(2) The acidic composition for reactive treatment according to the above (1), wherein the carboxylic acid compound is a citric acid compound.

(3) The acidic composition according to (1) or (2) , wherein the first ratio is 0.1 or more and 0.6 or less.

(4) The acidic composition according to (1) or (2) , wherein the first ratio is 0.2 or more and 0.4 or less.

(5) The acidic composition for reactive treatment according to the above (1), wherein the carboxylic acid compound is oxalic acid.

(6) The acidic composition according to (1) or (5) , wherein the second ratio is 0.1 or more and 1.7 or less.

(7) The acidic composition according to (1) or (5), wherein the second ratio is 1 or more and 2 or less .

(8) water-soluble vanadium-containing material does not contain an organic component of the water-soluble substance and film-forming property contains fluorine, (1) to (7) acidic composition of the placing serial to any one of.

(9) An acidic composition for reactive chemical conversion treatment that does not contain a water-soluble cobalt-containing substance, and a water-soluble trivalent chromium-containing substance that is 0.01 mol / L or more and 0.1 mol / L or less in terms of chromium, and titanium Containing 0.0001 mol / L or more and 1 mol / L or less of a water-soluble titanium-containing substance in terms of conversion, and 0.001 mol / L or more and 0.2 mol / L or less of a carboxylic acid compound in terms of carboxylic acid, 1 or 2 or more types selected from the group consisting of a citric acid compound and an oxalic acid compound, and a water content of the citric acid compound in terms of citric acid (unit: mol / L) in the acidic composition The first ratio, which is the ratio with respect to the chromium equivalent content (unit: mol / L) of the functional trivalent chromium-containing substance, is 0.05 or more and 0.8 or less, and / or the acid In the composition, the second ratio which is the ratio of the oxalic acid equivalent content (unit: mol / L) of the oxalic acid compound to the chromium equivalent content (unit: mol / L) of the water-soluble trivalent chromium-containing substance is 0. and at .05 to 2, further containing 0.001 mol / L or more 1 mol / L or less of the organic phosphonic acid compound in phosphorus terms, anti応型chemical conversion treatment for acidic composition.

(10) further containing the following water-soluble zinc-containing substance 0.005 mol / L or more 0.1 mol / L zinc terms above (1) from the acid composition according to any one of (9).

(11) An acidic composition for reactive chemical conversion treatment that does not contain a water-soluble cobalt-containing substance, and contains a water-soluble trivalent chromium-containing substance having a molar equivalent of 0.01 mol / L to 0.1 mol / L, and titanium Containing 0.0001 mol / L or more and 1 mol / L or less of a water-soluble titanium-containing substance in terms of conversion, and 0.001 mol / L or more and 0.2 mol / L or less of a carboxylic acid compound in terms of carboxylic acid, 1 or 2 or more types selected from the group consisting of a citric acid compound and an oxalic acid compound, and a water content of the citric acid compound in terms of citric acid (unit: mol / L) in the acidic composition The first ratio, which is the ratio to the chromium equivalent content (unit: mol / L) of the functional trivalent chromium-containing substance, is 0.05 or more and 0.8 or less, and / or The second ratio, which is the ratio of the oxalic acid equivalent content (unit: mol / L) of the oxalic acid compound to the chromium equivalent content (unit: mol / L) of the water-soluble trivalent chromium-containing substance in the composition. An acidic composition for reaction-type chemical conversion treatment, further containing a water-soluble aluminum-containing material of 0.0501 or more and 2 or less and 0.0001 mol / L or more and 1 mol / L or less in terms of aluminum.

(12) A contact step of bringing the acidic composition according to any of (1) to (11) above into contact with a substrate having a metal-based surface to form a chemical conversion film on the metal-based surface of the substrate. And a step of cleaning the base material that has undergone the contacting step to obtain a member that has the chemical conversion film on its surface. A method for producing a member that has a chemical conversion film on its surface.

(13) The metal-based surface was formed from a zinc-based plating film surface formed from a chloride bath, a film surface obtained by baking a zinc-based plating film formed from a zincate bath, and a zincate bath. The method for producing a member according to (12) , which is any one of the surfaces of a zinc-based plating film that has not been baked.

(14) An acidic composition for reactive chemical conversion treatment that does not contain a water-soluble cobalt-containing substance, and contains a water-soluble trivalent chromium-containing substance of 0.01 mol / L or more and 0.1 mol / L or less in terms of chromium, and titanium Containing 0.0001 mol / L or more and 1 mol / L or less of a water-soluble titanium-containing substance in terms of conversion, and 0.001 mol / L or more and 0.2 mol / L or less of a carboxylic acid compound in terms of carboxylic acid, 1 or 2 or more types selected from the group consisting of a citric acid compound and an oxalic acid compound, and a water content of the citric acid compound in terms of citric acid (unit: mol / L) in the acidic composition The first ratio, which is the ratio to the chromium equivalent content (unit: mol / L) of the functional trivalent chromium-containing substance, is 0.05 or more and 0.8 or less, and / or The second ratio, which is the ratio of the oxalic acid equivalent content (unit: mol / L) of the oxalic acid compound to the chromium equivalent content (unit: mol / L) of the water-soluble trivalent chromium-containing substance in the composition. A contact step in which an acidic composition for reactive chemical conversion treatment that is 0.05 or more and 2 or less is brought into contact with a substrate having a metal-based surface to form a conversion coating on the metal-based surface of the substrate; Cleaning the base material that has undergone the contact step to obtain a member having the chemical conversion film on the surface thereof, and the metal-based surface is a zinc-based plating film formed from a zincate bath, and is baked A method for producing a member comprising a chemical conversion film on the surface of the film obtained as described above, wherein the carboxylic acid compound contains the oxalic acid compound.

(15) contacting the acidic composition according to any one of (1) to (11) above with a base material having a metal surface to form a chemical conversion film on the metal surface of the base material. A method of using an acidic composition comprising.

(16) The metal-based surface was formed from a zinc-based plating film surface formed from a chloride bath, a film surface obtained by baking a zinc-based plating film formed from a zincate bath, and a zincate bath. The method for using an acidic composition according to (15) above , which is one of the surfaces of a zinc-based plating film that has not been baked.

(17) the metallic surface is a surface of the film obtained by baking a zinc-based plated film formed from a zincate bath, the carboxylic acid compound comprises the oxalic acid compound to the (16) Use of the acidic composition described.

  According to the present invention, it is possible to form a chemical conversion film having excellent corrosion resistance and consideration for environmental protection without using a water-soluble cobalt-containing substance that has been used frequently for forming a chemical conversion film having excellent corrosion resistance. A possible chemical conversion solution is provided. Moreover, the manufacturing method of a member provided with the chemical conversion film formed with this chemical conversion liquid on the surface is also provided.

Hereinafter, embodiments of the present invention will be described in detail.
1. Acid Composition for Reactive Chemical Treatment The composition of the acidic composition for reactive chemical treatment (also referred to as “chemical conversion solution” in this specification) according to an embodiment of the present invention will be described.

(1) Water-soluble trivalent chromium-containing substance The chemical conversion treatment liquid according to an embodiment of the present invention 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.

  It is possible to produce a water-soluble trivalent chromium-containing material in water as a material blended to contain the water-soluble trivalent chromium-containing material in the chemical conversion treatment liquid, that is, as a raw material for the water-soluble trivalent chromium-containing material. It is preferable to use a water-soluble compound (hereinafter referred to as “water-soluble trivalent chromium compound”).

  Examples of 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. In addition, since the hexavalent chromium compound is not positively added as a raw material with respect to the chemical conversion liquid which concerns on this embodiment, the chemical conversion liquid which concerns on this embodiment does not contain hexavalent chromium substantially.

  The content of the water-soluble trivalent chromium-containing substance in the chemical conversion treatment liquid according to the present embodiment is preferably 0.01 mol / L or more in terms of chromium from the viewpoint of improving the ease of forming a chemical conversion film, and 0 0.02 mol / L or more is more preferable, and 0.04 mol / L or more is particularly preferable. The upper limit of the content is not particularly limited, but if it is contained excessively, there is a risk of causing problems from the viewpoint of economy and waste liquid treatment, so the upper limit is about 0.15 mol / L in terms of chromium. The upper limit is more preferably about 0.12 mol / L, and the upper limit is more preferably about 0.1 mol / L.

(2) Water-soluble titanium-containing substance The chemical conversion treatment liquid according to this embodiment contains at least one water-soluble titanium-containing substance. The water-soluble titanium-containing substance is selected from the group consisting of titanium ions (Ti ³⁺ , Ti ⁴⁺ ) and water-soluble substances containing the same.

  A water-soluble compound capable of producing a water-soluble titanium-containing material in water (hereinafter referred to as “a water-soluble titanium-containing material”) It is preferable to use a “water-soluble titanium compound”.

To illustrate water-soluble titanium compounds, use Ti carbonates, oxides, hydroxides, nitrates, sulfates, phosphates, fluorides, fluoro acids (salts), organic acid salts, organic complex compounds, etc. Can do. Specifically, titanium oxide (IV) (titania), titanium nitrate, titanium sulfate (III), titanium sulfate (IV), titanyl sulfate TiOSO ₄ , titanium fluoride (III), titanium fluoride (IV), hexafluoro Titanate H ₂ TiF ₆ , ammonium hexafluorotitanate [(NH ₄ ) ₂ TiF ₆ ], titanium laurate, diisopropoxytitanium bisacetone (C ₅ H ₇ O ₂ ) ₂ Ti [OCH (CH ₃ ) ₂ ] ₂ , titanium acetylacetonate Ti (OC (═CH ₂ ) CH ₂ COCH ₃ ) _{3 and the} like. These may be anhydrides or hydrates. In addition, since it is preferable that the chemical conversion liquid which concerns on this embodiment is a chemical conversion liquid with little environmental impact, it is preferable that a water-soluble titanium compound does not contain a fluorine.

  The content of the water-soluble titanium-containing substance in the chemical conversion treatment liquid according to this embodiment is preferably 0.0001 mol / L or more in terms of titanium from the viewpoint of improving the ease of formation of the chemical conversion film, and is preferably 0.0005 mol. / L or more is more preferable, and 0.001 mol / L or more is particularly preferable. The upper limit of the content is not particularly limited, but adding too much increases the possibility of lowering the stability of the chemical conversion treatment liquid, or may cause problems from the viewpoint of economy and waste liquid treatment. In order to increase it, it is preferable that the upper limit is about 1 mol / L in terms of titanium, more preferably about 0.5 mol / L, and particularly preferably about 0.1 mol / L.

(3) Carboxylic acid compound The chemical conversion treatment liquid according to this embodiment contains a carboxylic acid compound. In this specification, the “carboxylic acid compound” is composed of one or more selected from the group consisting of a carboxylic acid, which is an organic acid having a carboxyl group, and ions, salts, derivatives and coordination compounds thereof. The compound in the state melt | dissolved in the chemical conversion liquid which is a composition is meant.

  As the carboxylic acid that gives the carboxylic acid compound according to the present embodiment, monocarboxylic acids such as formic acid, acetic acid, propionic acid; oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, Dicarboxylic acids such as sebacic acid, maleic acid, phthalic acid and terephthalic acid; tricarboxylic acids such as tricarbaric acid and aconitic acid; hydroxycarboxylic acids such as glycolic acid, lactic acid, malic acid, tartaric acid, citric acid, isocitric acid and ascorbic acid And aminocarboxylic acids such as glycine and alanine.

  The carboxylic acid compound according to this embodiment may contain one or more selected from the group consisting of a citric acid compound and an oxalic acid compound. Here, the “citric acid compound” is one or more selected from the group consisting of citric acid and its ions, salts, derivatives, and coordination compounds, and is contained in the chemical conversion treatment liquid that is an aqueous composition. A compound in a dissolved state is meant. The “oxalic acid compound” is one or more selected from the group consisting of oxalic acid and its ions, salts, derivatives, and coordination compounds, and is dissolved in a chemical conversion treatment solution that is an aqueous composition. Means a compound in the state.

  The carboxylic acid compound contained in the chemical conversion liquid according to the present embodiment may include one of a citric acid compound and an oxalic acid compound, or may include both. When the surface to be treated is made of a zinc-based plating film (referred to as a generic term for a zinc plating film and a zinc alloy plating film in the present specification) formed from a chloride bath, the chemical conversion treatment liquid according to this embodiment is used. The carboxylic acid compound contained in may contain at least one of a citric acid compound and an oxalic acid compound, and preferably consists of either one. When the surface to be treated is made of a film obtained by baking a zinc-based plating film formed from a zincate bath, the carboxylic acid compound contained in the chemical conversion treatment liquid according to this embodiment includes an oxalic acid compound. It is preferable that it consists of an oxalic acid compound. When the surface to be treated is a zinc-based plating film formed from a zincate bath and not subjected to baking treatment, the carboxylic acid compound contained in the chemical conversion treatment liquid according to the present embodiment includes a citric acid compound and It may contain at least one of oxalic acid compounds, and preferably consists of either one.

  A water-soluble compound capable of producing a carboxylic acid compound in water (hereinafter referred to as “carboxylic acid source”) as a material compounded to contain the carboxylic acid compound in the chemical conversion liquid, that is, a raw material of the water-soluble carboxylic acid compound It is preferable to use. Specific examples of the carboxylic acid source include carboxylic acid derivatives such as carboxylic acid esters, carboxylic acids, carboxylic acid salts (metal salts), and the like. The carboxylic acid source may be a carboxylic acid salt from the viewpoint of improving the solubility and ease of interaction between the generated carboxylic acid compound and other components contained in the chemical conversion treatment liquid. Examples of such carboxylates include sodium oxalate, sodium citrate, potassium oxalate, and potassium citrate.

  The content of the carboxylic acid compound in the chemical conversion treatment liquid according to the present embodiment is preferably 0.001 mol / L or more in terms of carboxylic acid from the viewpoint of improving the ease of formation of the chemical conversion film, and is 0.004 mol / L or more is more preferable, and 0.008 mol / L or more is particularly preferable. The upper limit of the content is not particularly limited, but adding too much increases the possibility of lowering the stability of the chemical conversion treatment liquid, or may cause problems from the viewpoint of economy and waste liquid treatment. Therefore, the upper limit is preferably about 0.4 mol / L, more preferably about 0.2 mol / L, and particularly preferably about 0.1 mol / L.

  The ratio (first ratio) of the citric acid compound content (unit: mol / L) in the chemical conversion solution according to the present embodiment to the content (unit: mol / L) of the water-soluble trivalent chromium-containing substance Is preferably from 0.05 to 0.8 from the viewpoint of facilitating the formation of a chemical conversion film having excellent corrosion resistance, more preferably from 0.1 to 0.6. It is particularly preferable to set it to 2 or more and 0.4 or less. The ratio (second ratio) of the oxalic acid compound content (unit: mol / L) to the content (unit: mol / L) of the water-soluble trivalent chromium-containing substance in the chemical conversion solution according to the present embodiment Is preferably in the range of 0.05 or more and 2.0 or less from the viewpoint of facilitating the formation of a chemical conversion film having excellent corrosion resistance, more preferably 0.1 or more and 1.7 or less. It is especially preferable to set it to 6 or more and 1.7 or less.

  In addition, the chemical conversion liquid which concerns on this embodiment may contain organic acid compounds other than said carboxylic acid compound. Examples of the organic acid related to such an organic acid compound include sulfonic acid. Although content of these organic acid compounds in the chemical conversion liquid which concerns on this embodiment is not specifically limited, It is preferable to keep in the range which said carboxylic acid compound can function appropriately.

(4) Organic phosphonic acid compound The chemical conversion treatment liquid according to this embodiment may contain an organic phosphonic acid compound. Here, “organic phosphonic acid compound” means a compound composed of one or more selected from the group consisting of organic phosphonic acid and its ions and salts, and “organic phosphonic acid” means that the formula is R—P (= O) (OH) ₂ (R is an organic group), which means an organic group bonded to a phosphonic group. By containing the organic phosphonic acid compound, the amount of metal dissolved from the chemical conversion film formed from the chemical conversion treatment liquid, particularly the amount of chromium dissolved can be reduced.

  As 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).

  As 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.

  In the case where the chemical conversion treatment liquid according to the present embodiment contains an organic phosphonic acid compound, the content thereof is set to 0.001 mol / L or more in terms of phosphorus from the viewpoint of facilitating formation of a chemical conversion film having excellent characteristics. It is preferably 0.005 mol / L or more, more preferably 0.01 mol / L or more. The upper limit of the content is not particularly limited, but adding too much increases the possibility of reducing the appearance of the obtained chemical conversion film, or may cause problems from the viewpoint of economy and waste liquid treatment. In order to increase it, it is preferable that the upper limit is about 1 mol / L in terms of phosphorus, and more preferably about 0.1 mol / L. From the viewpoint of improving the appearance of the obtained chemical conversion film, it may be preferable that the chemical conversion treatment liquid according to this embodiment does not substantially contain an organic phosphonic acid compound.

(5) Water-soluble zinc-containing substance As described above, when the chemical conversion treatment liquid according to the present embodiment contains an organic phosphonic acid compound, the chemical conversion treatment liquid according to the present embodiment is at least one kind of water-soluble zinc. A contained substance may be further contained. The water-soluble zinc-containing substance is selected from the group consisting of zinc ions (Zn ²⁺ ) and water-soluble substances containing the same. When the chemical conversion treatment liquid according to the present embodiment contains an organic phosphonic acid compound, it is possible to further improve the stability of the quality of the chemical conversion film formed from the chemical conversion treatment liquid by further containing a water-soluble zinc-containing substance. There are cases where it is possible.

  A water-soluble compound (hereinafter referred to as “a water-soluble zinc-containing material”) that is capable of producing a water-soluble zinc-containing material in water as a raw material for the water-soluble zinc-containing material, It is preferable to use a “water-soluble zinc compound”.

  Examples of water-soluble zinc compounds include compounds such as zinc chloride, zinc carbonate, zinc oxide, zinc borate, zinc acetate, zinc sulfate, and zinc nitrate. The water-soluble zinc compound may be composed of only one kind of compound, or may be composed of a plurality of kinds.

  In the case where the chemical conversion treatment liquid according to the present embodiment contains a water-soluble zinc-containing substance, the content thereof is preferably 0.005 mol / L or more in terms of zinc from the viewpoint of ease of formation of the chemical conversion film. , 0.01 mol / L or more is more preferable, and 0.015 mol / L or more is particularly preferable. The upper limit of the content is not particularly limited, but adding too much increases the possibility of lowering the stability of the chemical conversion treatment liquid, or may cause problems from the viewpoint of economy and waste liquid treatment. Therefore, the upper limit is preferably about 0.1 mol / L in terms of zinc, more preferably about 0.075 mol / L, and particularly preferably about 0.05 mol / L. preferable.

(6) Other components In addition to the above substances, the chemical conversion treatment liquid according to the present embodiment includes a water-soluble metal-containing substance related to a metal other than the above metals (Cr, Zn and Ti), an inorganic acid and an anion thereof, You may include 1 type, or 2 or more types chosen from the group which consists of an inorganic colloid, a silane coupling agent, and an organic phosphorus compound. Polyphenols such as pyrogallol and benzenediol; corrosion inhibitors; surfactants such as diols, triols, and amines; plastic dispersions; coloring materials such as dye formers such as dyes, pigments, and metal dye formers; desiccants and dispersions One or more components selected from the group consisting of agents may be further contained.

  The chemical conversion treatment liquid according to the present embodiment does not substantially contain a water-soluble substance containing fluorine from the viewpoint of reducing the influence on the environment. Moreover, since the chemical conversion treatment by the chemical conversion treatment liquid according to the present embodiment is a reaction type, it does not substantially contain a film-forming organic component.

  As metal elements contained in the water-soluble metal-containing substance related to the metal other than the above metals (Cr, Zn and Ti), Ni, Na, K, Ag, Fe, Ca, Mg, Sc, Mn, Cu, Sn, Mo, Al and W are exemplified, and may be present in the form of oxyacid ions such as tungstate ions or may be present in the form of coordination compounds. An additional effect may be acquired by containing these water-soluble metal containing substances. For example, when a water-soluble aluminum-containing substance is contained, the appearance of the resulting chemical conversion film is improved, or the film properties such as corrosion resistance and the amount of dissolved metal are dependent on the substrate (for example, a bath for forming a zinc-based plating). The film characteristics can be easily changed when the types of are different).

  The content of the water-soluble metal-containing material is not particularly limited. It is set as appropriate according to the role of the metal element contained in each water-soluble metal-containing substance. For example, in the case of a water-soluble aluminum-containing substance, it is preferably 0.0001 mol / L or more, more preferably 0.0005 mol / L or more, and more preferably 0.001 mol / L or more in terms of aluminum. Particularly preferred. The upper limit of the content is not particularly limited, but adding too much increases the possibility of lowering the stability of the chemical conversion treatment liquid, or may cause problems from the viewpoint of economy and waste liquid treatment. In order to increase it, it is preferable that the upper limit is about 1 mol / L in terms of aluminum, more preferably about 0.5 mol / L, and more preferably about 0.1 mol / L.

  In addition, the chemical conversion liquid which concerns on this embodiment does not contain the water-soluble cobalt containing substance which is anxious about the influence on an environment. Moreover, from the chemical conversion film containing V, the amount of elution of V may be excessively increased. In this case, there is a concern about the influence of the eluted V on the environment. Is substantially free of water-soluble vanadium-containing materials.

  Inorganic acids include hydrohalic acids other than fluorine, such as hydrochloric acid and hydrobromic acid, chloric acid, perchloric acid, chlorous acid, hypochlorous acid, sulfuric acid, sulfurous acid, nitric acid, nitrous acid, and phosphoric acid (Orthophosphoric acid), polyphosphoric acid, metaphosphoric acid, pyrophosphoric acid, ultraphosphoric acid, hypophosphorous acid, and superphosphoric acid are exemplified, and hydrohalic acid other than fluorine, sulfuric acid, nitric acid and phosphoric acid (orthophosphoric acid) It is preferable that 1 type (s) or 2 or more types selected from the group consisting of is contained as an anion.

  The concentration in the chemical conversion solution of these inorganic acids and / or inorganic acid ions is not particularly limited. Generally, the ratio of the total molar concentration of the inorganic acid and the inorganic acid ion to the total molar concentration in terms of metal of the water-soluble metal-containing substance is 0.1 or more and 10 or less, preferably 0.5 or more and 3 or less. It is.

  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 γ-methacryloxypropyltrimethoxysilane.

(7) Solvent, pH
The solvent of the chemical conversion treatment liquid according to the present embodiment contains water as a main component. As a solvent other than water, an organic solvent having high solubility in water, such as alcohol, ether, and ketone, may be mixed. In this case, it is preferable that 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.

  Moreover, the chemical conversion liquid which concerns on this embodiment is made acidic from a viewpoint of advancing chemical conversion, Therefore pH is set to less than seven. The preferable value of pH within the acidic range is not particularly limited. Appropriately considering the possibility that the formation of the chemical conversion film will be non-uniform if the pH is excessively low, and the possibility that the stability of the chemical conversion solution will decrease if the pH is excessively high. You only have to set it. From the viewpoint of improving the quality of the chemical conversion film and the stability of the chemical conversion treatment liquid, the preferred pH is 1 or more and 5 or less, and more preferably 1.5 or more and 3 or less.

2. Concentrated composition for preparing chemical conversion liquid A liquid composition 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 prepared. In this case, it is preferable because the labor for preparing the contents of the respective components can be saved and the storage is easy. When preparing this concentrated solution for chemical conversion treatment, the upper limit is set for the content in consideration of the solubility of each of the above components.

3. Substrate on which the chemical conversion treatment is performed The material of the base material on which the chemical conversion treatment according to the present embodiment is performed is not particularly limited as long as it has a metal surface that can form a chemical conversion film using the chemical conversion treatment liquid according to the present embodiment. A preferable material is a metal material, and a steel plate on which zinc-based plating is applied is particularly preferable. The plating method may be electroplating or hot dipping. In the case of hot dipping, alloying may be performed after plating.

  The composition of the above zinc-based plating may be pure zinc or a zinc alloy. In the case of zinc alloy plating, iron, nickel and aluminum are exemplified as the alloy metal. The plating method may be electroplating or hot dipping. In the case of electroplating, any of a cyan bath, a chloride bath, a sulfuric acid bath and a zincate bath may be used, and a baking treatment may be performed after the formation of the plating film. In the case of hot dipping, alloying treatment may be performed after plating.

4). The manufacturing method of the member which equips the surface with a chemical conversion film The manufacturing method of the member which provides the chemical conversion film on the surface using the chemical conversion liquid which concerns on this embodiment is demonstrated.

  The manufacturing method according to the present embodiment includes a contact step of bringing the chemical conversion treatment liquid according to the present embodiment into contact with a base material having a metal-based surface, and forming a chemical conversion film on the metal-based surface of the base material. And a cleaning step of cleaning the base material that has undergone the step to obtain a member having a chemical conversion film on the surface thereof.

  In the contacting step, the method for bringing the chemical conversion treatment liquid according to the present embodiment into contact with the substrate having a metal-based surface is not particularly limited. The simplest method is immersion, but spraying or application using a roll or the like may also be used. The contact conditions (contact temperature, contact time) are not particularly limited, and may be appropriately set in consideration of the composition of the chemical conversion treatment liquid, the composition of the material constituting the substrate surface, productivity, and the like. When the temperature of the chemical conversion treatment liquid is from room temperature to about 40 ° C., it is often brought into contact for about 10 seconds to 5 minutes. In addition, since the chemical conversion liquid which concerns on this embodiment is a reaction type chemical conversion liquid, even if time is lengthened too much, the thickness of a chemical conversion film does not usually become thick according to time.

  The substrate to be subjected to the contacting step is washed (for example, degreased and rinsed) by a known method, and further contacted with an aqueous acid solution (for example, an aqueous nitric acid solution of about several ml / L) (room temperature, about 10 seconds). An activation treatment may be performed.

  The base material that has undergone the contact step is washed using, for example, water. This point is different from a so-called coating-type chemical conversion treatment liquid, and is a process performed because the chemical conversion treatment liquid according to the present embodiment is a reactive chemical conversion treatment liquid. By this step, the chemical conversion treatment solution remaining on the surface of the base material that has undergone the contact step is washed away, and a member including the base material and the chemical conversion film formed on the surface thereof is obtained. The member after washing is usually subjected to a drying step for the purpose of removing moisture adhering to the chemical conversion film and the substrate. Drying conditions (drying temperature, drying time) are not particularly limited. It is appropriately set in consideration of the heat resistance and productivity of the substrate. It may be dried by standing for about 10 minutes in an oven maintained at a temperature of about 100 ° C. or lower, or it may be dried using a centrifuge, and it should be left in a normal environment. May be dried. Depending on the type of chemical conversion film, there may be a change in composition during drying, for example, a change to a part or all of the hydroxide.

  In the manufacturing method according to the present embodiment, after the above-described member is treated with the chemical conversion treatment liquid according to the present embodiment to form a chemical conversion film, a treatment with a finishing agent is performed to improve corrosion resistance and scratch resistance. A finishing treatment step for forming a finish film may be provided. The relationship between the finishing process and the drying process is arbitrary, and the drying process may be performed after the finishing process after the cleaning process, or the finishing process may be performed after the drying process after the cleaning process.

  As specific examples of the metal-based surface of the base material to be treated, the surface of the zinc-based plating film formed from the chloride bath, the surface of the film obtained by baking the zinc-based plating film formed from the zincate bath, And a zinc-based plating film formed from a zincate bath and not subjected to baking treatment. When the surface to be treated is a surface of a zinc-based plating film formed from a chloride bath or a surface of a zinc-based plating film formed from a zincate bath that has not been baked, the carboxylic acid compound is a citric acid compound. The carboxylic acid compound is preferably composed of a citric acid compound or an oxalic acid compound. When the metal-based surface is a zinc-based plating film formed from a zincate bath and is a surface of a film obtained by baking, the carboxylic acid compound preferably contains an oxalic acid compound, and consists of an oxalic acid compound. It is more preferable.

5. Method for Using Chemical Conversion Film A method for using the chemical conversion treatment liquid according to this embodiment will be described.
The usage method which concerns on this embodiment contacts the acidic composition which is a chemical conversion liquid which concerns on this embodiment with the base material which has a metal-type surface, and forms a chemical conversion film on the metal-type surface of this base material. Including that. The relationship between the metal-based surface of the base material serving as the surface to be treated and the carboxylic acid compound is the same as in the case of the method for producing a member provided with the above-described chemical conversion film on the surface, and thus the description thereof is omitted.

  The embodiment described above is described for facilitating understanding of the present invention, and is not described for limiting the present invention. Therefore, each element disclosed in the above embodiment is intended to include all design changes and equivalents belonging to the technical scope of the present invention.

  Hereinafter, although the effect of the present invention is explained based on an example, the present invention is not limited to this.

Example 1
1. Preparation of test member A chemical conversion treatment liquid having the basic composition shown in Table 1 and the detailed composition shown in Table 2 was prepared. In addition, as for chemical conversion liquid 1-25, the titanium conversion compounding quantity of the water-soluble titanium compound was 0.001 mol / L, and the aluminum conversion compounding quantity of the water-soluble aluminum compound was 0.001 mol / L.

  In Table 1, “source of carboxylic acid and the like” means a generic term for a carboxylic acid source and a water-soluble compound capable of generating an organic acid compound in water. The “water-soluble additive metal compound” is a water-soluble metal compound that is a substance blended to contain a water-soluble metal-containing substance in the chemical conversion treatment liquid, other than the water-soluble trivalent chromium compound and the water-soluble zinc compound. Means things. The organic phosphonic acid compound was “Dequest 2010” manufactured by Thermophos Japan.

“Additive metal” in Table 2 means a metal related to the water-soluble additive metal compound in Table 1. Moreover, the kind of the water-soluble metal compound which concerns on each metal was as follows.
Co: Cobalt nitrate Ni: Nickel chloride Ti: Titanyl sulfate V: Sodium vanadate Al: Aluminum nitrate

A base material made of steel M10 bolts was subjected to galvanizing treatment under the following conditions to obtain a base material having a galvanized film on its surface.
Zinc plating composition: Chloride bath (Ammonkali eclectic bath)
Plating temperature: 30 ° C
Plating time: 1800 seconds Electrolysis condition: 1.5 A / dm ²

  Rinsing was performed by immersing the galvanized substrate in pure water at 23 ° C. for 10 seconds while oscillating the substrate. The substrate after the galvanizing treatment that had been rinsed was immersed in a dilute nitric acid aqueous solution (3 ml / L) at 23 ° C. for 10 seconds while oscillating the substrate for 10 seconds to perform the activation treatment. The substrate taken out from the dilute nitric acid aqueous solution was rinsed by immersing the substrate in pure water at 23 ° C. for 10 seconds while rocking the substrate.

  By immersing the substrate after the activation treatment after rinsing in any one of the above-described chemical conversion liquids 1-1 to 1-25 maintained at 30 ° C. for 45 seconds while rocking the substrate, chemical conversion is performed. Processed. The base material taken out from the chemical conversion solution was rinsed by immersing the base material in pure water at 23 ° C. for 10 seconds while rocking the base material. The base material after the chemical conversion treatment after rinsing was dried by being left in an oven maintained at 80 ° C. for 10 minutes. In this way, the member in which the chemical conversion film was formed on the surface was obtained as test members 1-1 to 1-25.

2. Evaluation of test member (1) Evaluation of corrosion resistance The obtained test members 1-1 to 1-25 were subjected to a neutral salt spray test for 96 hours in accordance with JIS Z2371: 2000 (ISO 9227: 1990). The surface of the subsequent test member was visually observed, the area where white rust was generated was measured, the ratio to the area of the main surface of the test member was measured, and the white rust area ratio (unit:%) was determined.

(2) Measurement of dissolution amount One test member (surface area: 25 cm ² ) was immersed in 100 ml of pure water for 24 hours. Thereafter, the test member was taken out, and the amount of metal dissolved in water was measured using ICP (SPS5520 manufactured by SII Nano Technology Co., Ltd.) to determine the amount dissolved (unit: μg / cm ² ).

(3) Appearance (3-1) Color Tone The surface made of the chemical conversion film of the test member was visually observed and evaluated for color tone.

(3-2) Gloss / Uniformity The surface of the test member was visually observed, and the uniformity of gloss and appearance was evaluated according to the following criteria.
A (excellent): glossy and no cloudiness is observed, and the entire surface has a uniform appearance B (good): some cloudiness is observed and / or the gloss is slightly weak C (good): cloudiness is present, Low gloss and / or slightly uniform appearance D (Poor): Highly cloudy, no gloss and / or uneven appearance

3. Results Table 2 shows the evaluation results. As shown in Table 2, when the chemical conversion treatment liquid contains a water-soluble titanium-containing substance and a carboxylic acid compound (chemical conversion treatment liquids 1-4, 1-10, 1-16 and 1-22), The chemical conversion film (this chemical conversion film) formed from the treatment liquid has corrosion resistance equivalent to or better than that of a chemical conversion film (Co-containing chemical conversion film) formed from a chemical conversion treatment liquid containing a water-soluble cobalt-containing substance. It was. In addition, the amount of metal dissolved was equivalent to that of the Co-containing chemical film, and the possibility of affecting the environment was low from the viewpoint of metal dissolution from the chemical film.

  On the other hand, when the metal related to the water-soluble metal-containing substance contained in the chemical conversion treatment liquid is Ni or Al, the corrosion resistance of the obtained chemical conversion film is far inferior to the corrosion resistance of the Co-containing chemical conversion film. . When the metal related to the water-soluble metal-containing substance contained in the chemical conversion treatment liquid is V, the amount of metal dissolved is excessive, and there is a possibility of affecting the environment from the viewpoint of metal dissolution from the chemical conversion film. It was expensive.

(Example 2)
In the blending composition shown in Table 1, a water-soluble additive metal compound is not blended, and the blending amount of citric acid as a source of carboxylic acid, etc. The ratio of the trivalent chromium-containing substance to the chromium equivalent content (unit: mol / L) (in the examples, this ratio is also referred to as “CA1 / Cr ratio”) is changed to the value shown in Table 3. Chemical conversion liquids 2-1 to 2-13 were obtained. Moreover, in the compounding composition shown in Table 1, the compounding amount of oxalic acid as a source of carboxylic acid and the like is not blended with the water-soluble additive metal compound, and the oxalic acid compound content (unit: mol / L) The ratio of the water-soluble trivalent chromium-containing substance to the chromium equivalent content (unit: mol / L) (this ratio is also referred to as “CA2 / Cr ratio” in the examples) is changed to the value shown in Table 3. Thus, chemical conversion liquids 2-14 to 2-27 were obtained.

Thereafter, in the same manner as in Example 1, test members 2-1 to 2-27 corresponding to the chemical conversion liquids 2-1 to 2-27 were obtained.
When the obtained test members 2-1 to 2-27 are subjected to a neutral salt spray test in accordance with JIS Z2371: 2000 (ISO 9227: 1990), and the test time is 48 hours, the case is 72 hours And the surface of the test member in the case of 96 hours was observed visually, and the white rust area ratio (unit:%) in each time was determined.
As a result, as shown in Table 2, it was confirmed that the white rust area ratio fluctuated by changing the CA1 / Cr ratio or the CA2 / Cr ratio.

(Example 3)
As shown in Table 4, using the chemical conversion treatment liquid prepared in Example 1, the same operation as in Example 1 was performed to prepare test members 3-1 to 3-15.

  A steel M10 bolt 1 kg as a dummy and 1 kg of each of the test members 3-1 to 3-15 are put into an auto gilder and rotated for 2 minutes. It was.

  A neutral salt spray test is performed on the test member in accordance with JIS Z2371: 2000 (ISO 9227: 1990). When the test time is 72 hours, 120 hours, 168 hours, and 216 hours The surface of the test member was visually observed, and the white rust area ratio (unit:%) at each time was determined.

Further, one test member (surface area: 25 cm ² ) was immersed in 100 ml of pure water for 24 hours. Thereafter, the test member was taken out, and the amount of metal dissolved in water was measured using ICP (SK-150, manufactured by New Kyoritsu Chemical Co., Ltd.) to determine the amount dissolved (unit: μg / cm ² ).

  As a result, for the test members 3-3, 3-8, and 3-13 obtained from the chemical conversion liquids 1-4, 1-10, and 1-22 containing the water-soluble titanium-containing substance, the corrosion resistance and the metal dissolution amount Each of these is equivalent to the test members (3-2, 3-7 and 3-12) obtained from the chemical conversion liquids (1-2, 1-8 and 1-20) containing a water-soluble cobalt-containing substance. Or better than that. On the other hand, when the water-soluble metal-containing substance contained in the chemical conversion treatment liquid is other than the water-soluble titanium-containing substance, the water-soluble cobalt-containing substance is used in at least one of the corrosion resistance and the metal dissolution amount of the obtained chemical conversion film. The result was remarkably inferior to the test member obtained from the chemical conversion treatment solution contained.

Example 4
A chemical conversion treatment liquid 4 obtained by removing zinc oxide and an organic phosphonic acid compound as water-soluble zinc compounds from the chemical conversion treatment liquid 1-4 prepared in Example 1 was prepared.
Using this chemical conversion liquid 4 and chemical conversion liquid 1-4, the same operation as in Example 1 was carried out to produce two types of test members having chemical conversion films. About these test members, the neutral salt spray test similar to Example 1 and the neutral salt spray test after brazing similar to Example 3 were performed, and the white rust area ratio at the test time of 72 hours and 120 hours ( Unit:%) was measured. For these test members, the amount of dissolved metal was measured in the same manner as in Example 1. The results are shown in Table 5.

(Example 5)
In the blending composition shown in Table 1, 0.001 mol / L of a water-soluble titanium compound as a water-soluble additive metal compound is blended in terms of titanium, and the CA1 / Cr ratio or CA2 / Cr ratio is the value shown in Table 6. Then, the amount of citric acid or oxalic acid was changed to obtain chemical conversion liquids 5-1 to 5-8. Thereafter, in the same manner as in Example 1, test members 5-1 to 5-8 corresponding to the chemical conversion liquids 5-1 to 5-8 were obtained.

The surfaces of the obtained test members 5-1 to 5-8 were visually observed, and the uniformity of gloss and appearance was evaluated according to the determination criteria (A to D) of Example 1. In addition, a neutral salt spray test is performed on the obtained test members 5-1 to 5-8 in accordance with JIS Z2371: 2000 (ISO 9227: 1990). When the test time is 48 hours, 72 hours In this case, the surface of the test member in the case of 96 hours was visually observed, and the white rust area ratio (unit:%) at each time was determined.
As a result, as shown in Table 6, it was confirmed that the white rust area ratio fluctuated by changing the CA1 / Cr ratio or the CA2 / Cr ratio.

(Example 6)
In the compounding composition shown in Table 1, as the water-soluble additive metal compound, two compounds selected from the group consisting of a water-soluble titanium compound, a water-soluble aluminum compound, a water-soluble vanadium compound, and a water-soluble nickel compound are used. In addition to 0.001 mol / L in terms of metal contained in the chemical, the amount of citric acid or oxalic acid is changed so that the CA1 / Cr ratio or the CA2 / Cr ratio becomes the value shown in Table 6, and the chemical conversion treatment liquid 6-1 to 6-10 were obtained. Thereafter, in the same manner as in Example 1, test members 6-1 to 6-10 corresponding to the chemical conversion liquids 6-1 to 6-10 were obtained.

  The surfaces of the obtained test members 6-1 to 6-10 were visually observed, and the uniformity of gloss and appearance was evaluated according to the determination criteria (A to D) of Example 1. In addition, a neutral salt spray test was performed on the obtained test members 6-1 to 6-10 in accordance with JIS Z2371: 2000 (ISO 9227: 1990). When the test time was 48 hours, 72 hours In this case, the surface of the test member in the case of 96 hours was visually observed, and the white rust area ratio (unit:%) at each time was determined. The results are shown in Table 7.

Claims (14)

An acidic composition for reactive chemical conversion treatment that does not contain a water-soluble cobalt-containing substance,
A water-soluble trivalent chromium-containing substance of 0.02 mol / L or more and 0.1 mol / L or less in terms of chromium;
0.0001 mol / L or more and 1 mol / L or less of a water-soluble titanium-containing substance in terms of titanium,
Containing 0.001 mol / L or more and 0.2 mol / L or less carboxylic acid compound in terms of carboxylic acid,
The carboxylic acid compound includes one or more selected from the group consisting of a citric acid compound and an oxalic acid compound,
The first ratio, which is the ratio of the citric acid equivalent content (unit: mol / L) of the citric acid compound to the chromium equivalent content (unit: mol / L) of the water-soluble trivalent chromium-containing substance in the acidic composition Is 0.05 or more and 0.8 or less, and / or
In the acidic composition, a second ratio which is a ratio of the oxalic acid equivalent content (unit: mol / L) of the oxalic acid compound to the chromium equivalent content (unit: mol / L) of the water-soluble trivalent chromium-containing substance. There Ru der 0.05 or more and 2 or less,
An acidic composition for reactive chemical conversion treatment. Acid composition of claim 1 wherein the carboxylic acid compound is citric acid compound.   The acidic composition according to claim 1 or 2, wherein the first ratio is 0.1 or more and 0.6 or less.   The acidic composition according to claim 1 or 2, wherein the first ratio is 0.2 or more and 0.4 or less. Acid composition of claim 1 wherein the carboxylic acid compound is oxalic acid. The second ratio is 0.1 or more on 1. The acidic composition of Claim 1 or 5 which is 7 or less. The acidic composition according to claim 1 or 5, wherein the second ratio is 1 or more and 2 or less .   The acidic composition of any one of Claim 1 to 7 which does not contain the water-soluble vanadium containing substance and the water-soluble substance containing a fluorine. An acidic composition for reactive chemical conversion treatment that does not contain a water-soluble cobalt-containing substance ,
A water-soluble trivalent chromium-containing substance of 0.01 mol / L or more and 0.1 mol / L or less in terms of chromium;
0.0001 mol / L or more and 1 mol / L or less of a water-soluble titanium-containing substance in terms of titanium,
Containing 0.001 mol / L or more and 0.2 mol / L or less carboxylic acid compound in terms of carboxylic acid,
The carboxylic acid compound includes one or more selected from the group consisting of a citric acid compound and an oxalic acid compound,
The first ratio, which is the ratio of the citric acid equivalent content (unit: mol / L) of the citric acid compound to the chromium equivalent content (unit: mol / L) of the water-soluble trivalent chromium-containing substance in the acidic composition Is 0.05 or more and 0.8 or less, and / or
In the acidic composition, a second ratio which is a ratio of the oxalic acid equivalent content (unit: mol / L) of the oxalic acid compound to the chromium equivalent content (unit: mol / L) of the water-soluble trivalent chromium-containing substance. Is 0.05 or more and 2 or less,
Further containing 0.001 mol / L or more 1 mol / L or less of the organic phosphonic acid compound in phosphorus terms, anti応型chemical conversion treatment for acidic composition. Further containing the following water-soluble zinc-containing substance 0.005 mol / L or more 0.1 mol / L zinc terms, acidic composition according to any one of claims 1 to 9. An acidic composition for reactive chemical conversion treatment that does not contain a water-soluble cobalt-containing substance,
A water-soluble trivalent chromium-containing substance of 0.01 mol / L or more and 0.1 mol / L or less in terms of chromium;
0.0001 mol / L or more and 1 mol / L or less of a water-soluble titanium-containing substance in terms of titanium,
Containing 0.001 mol / L or more and 0.2 mol / L or less carboxylic acid compound in terms of carboxylic acid,
The carboxylic acid compound includes one or more selected from the group consisting of a citric acid compound and an oxalic acid compound,
The first ratio, which is the ratio of the citric acid equivalent content (unit: mol / L) of the citric acid compound to the chromium equivalent content (unit: mol / L) of the water-soluble trivalent chromium-containing substance in the acidic composition Is 0.05 or more and 0.8 or less, and / or
In the acidic composition, a second ratio which is a ratio of the oxalic acid equivalent content (unit: mol / L) of the oxalic acid compound to the chromium equivalent content (unit: mol / L) of the water-soluble trivalent chromium-containing substance. Is 0.05 or more and 2 or less,
Further containing 0.0001 mol / L or more and 1 mol / L or less of a water-soluble aluminum-containing substance in terms of aluminum,
An acidic composition for reactive chemical conversion treatment . Contacting the acidic composition according to any one of claims 1 to 11 with a substrate having a metal-based surface to form a chemical conversion film on the metal-based surface of the substrate;
A method for producing a member having a chemical conversion film on its surface, comprising: cleaning the base material that has undergone the contact step to obtain a member having the chemical conversion film on its surface.   The surface of a zinc-based plating film formed from a chloride bath, the surface of a film obtained by baking a zinc-based plating film formed from a zincate bath, and the zinc-based plating formed from a zincate bath The method for producing a member according to claim 12, wherein the member is one of the surfaces of a coating that is not baked. An acidic composition for reactive chemical conversion treatment that does not contain a water-soluble cobalt-containing substance,
A water-soluble trivalent chromium-containing substance of 0.01 mol / L or more and 0.1 mol / L or less in terms of chromium;
0.0001 mol / L or more and 1 mol / L or less of a water-soluble titanium-containing substance in terms of titanium,
Containing 0.001 mol / L or more and 0.2 mol / L or less carboxylic acid compound in terms of carboxylic acid,
The carboxylic acid compound includes one or more selected from the group consisting of a citric acid compound and an oxalic acid compound,
The first ratio, which is the ratio of the citric acid equivalent content (unit: mol / L) of the citric acid compound to the chromium equivalent content (unit: mol / L) of the water-soluble trivalent chromium-containing substance in the acidic composition Is 0.05 or more and 0.8 or less, and / or
In the acidic composition, a second ratio which is a ratio of the oxalic acid equivalent content (unit: mol / L) of the oxalic acid compound to the chromium equivalent content (unit: mol / L) of the water-soluble trivalent chromium-containing substance. Is 0.05 or more and 2 or less ,
The acid composition, the contacting step of contacting the substrate with a metal-based surface to form a conversion coating on the metallic surface of the substrate,
Cleaning the base material that has undergone the contact step, and obtaining a member that includes the chemical conversion film on the surface thereof ,
The metal-based surface is a zinc-based plating film formed from a zincate bath, which is a surface of a film obtained by baking treatment, and the carboxylic acid compound includes the oxalic acid compound and has a chemical conversion film on the surface. Manufacturing method of member.