JP2010518185A - Metal pretreated with luminescent pigment - Google Patents

Abstract

  The present invention relates to an aqueous agent containing a particulate inorganic pigment that emits light when irradiated with ultraviolet rays and having a pH value of 4 to 1 and having an extremely low chromium content for metal surface anticorrosion treatment. Concentrates for preparing the aqueous agent of the present invention or concentrates that can be used as they are for the treatment of metal surfaces are also included in the present invention. The method of the present invention comprises a step of treating a metal surface with such an aqueous agent, and light emission of the metal surface caused by the inorganic pigment of the present invention deposited and / or fixed on the metal base anticorrosive coating layer. Engineering the process quality by homogenizing as much as possible and optimizing the process and / or coating layer quality derived from these steps.

Description

  The present invention is in the field of chemical surface treatment of zinc or galvanized steel, aluminum, magnesium, or alloys thereof. The present invention is an aqueous agent substantially free of chromium for anticorrosion treatment of a metal surface containing a particulate inorganic pigment, wherein the pigment emits light (luminesce) when irradiated with ultraviolet light, and has a pH of 1. The present invention relates to an aqueous agent that is 4 or less. The invention also mainly encompasses concentrates that act as concentrates for the aqueous agents of the invention or that can be used directly as such to treat metal surfaces. The method according to the present invention comprises a step of treating a metal surface with the treatment agent, and illuminating the metal surface as uniformly as possible by impregnating and / or immobilizing the surface of the metal substrate with the inorganic pigment of the present invention. Optically assessing the quality of the processing process. The optical evaluation of the anticorrosion treatment, where the light emission of the treated metal surface preferably occurs in the visible light region and can be discerned with the naked eye, expands the possibilities of various post treatments. Such an optical evaluation is not possible in an industrial coating process without the presence of a luminescent pigment in the anticorrosive organic-inorganic hybrid layer and therefore forms a further aspect of the invention.

  Chemical treatment of metal surfaces to protect against corrosion substantially involves phosphate treatment and chemical conversion, the latter chemical conversion forming a very thin amorphous, mainly inorganic protective film. This treatment does not change the metal surface to be visible to the naked eye. The appearance of interference colors can only be observed for coating layer thicknesses above 100 nm. Due to the strong dependence of the interference color on the viewing angle, an overall uniform impression of the anticorrosion treated metal surface does not occur. Only by applying a chromate conversion coating as a passivating conversion treatment, a intensively colored metal surface is produced. Consequently, from years of experience with chromate conversion coatings on metal surfaces, those skilled in the art are accustomed to obtaining colored layers resulting from conversion treatments. At this time, those skilled in the art can visually recognize immediately whether the desired effect has been realized by the processing. Chromate conversion coatings must be effectively replaced with another conversion treatment that does not contain chromium due to the toxicity of the chemicals used and according to existing European guidelines (2000/53 / EC; 2005/673 / EC) Thus, there is a need for a treatment bath and treatment method that provides an optically visible improvement of the metal surface that represents each treatment. Expensive surface analysis inspection of colorless layers, for example by X-ray fluorescence measurement, is routinely applied, but this is very costly and has only the quality control properties of a random sample type.

  In the prior art, a typical anti-corrosion treatment method for a metal surface producing a colorless conversion treatment layer is described in WO 00/71626 and in the unpublished German patent application No. 102005059314.3. Are listed. “Metal surface conversion” is understood by those skilled in the art to mean the deposition of a protective film that is almost completely inorganic and amorphous, initiated by a corrosive action on the metal substrate. In this case, this conversion treatment layer is free from both anions and cations from the treatment agent and from the cations of the metal substrate which are dissolved away during the chemical conversion treatment of the surface by corrosion attack and are embedded in the layer to some extent. It is made up. In addition, most chemical conversion treatment baths contain organic polymer compounds. These organic polymer compounds usually exhibit complexing properties, but do not act exclusively to stabilize the bath components, but rather as a component of the chemical conversion treatment layer, to adhere to further deposited organic lacquer systems. It is chosen to have a favorable effect on it. Thus, the chemical conversion layer forms an organic-inorganic hybrid layer, and the organic components can vary greatly through the relevant composition of the chemical conversion agent and the manner in which the chemical conversion agent is applied.

In this regard, International Publication No. WO 00/71626 discloses a chromium-free anticorrosive, which is water and a) 0.5 to 100 g / liter of titanium (IV), silicon. (IV) and / or zirconium (IV) hexafluoride anion b) 0 to 100 g / liter of phosphoric acid c) 0 to 100 g / liter of cobalt, nickel, vanadium, iron, manganese, molybdenum or tungsten One or more of the compounds d) 0.5 to 30% by weight of at least one water-soluble and / or water-dispersible film-forming organic polymer or copolymer e) 0.1 to 10% by weight of organic phosphones Acid f) Optionally contains additional auxiliaries and additives.

  In this connection, since the chemical conversion treatment is performed by the “coating / drying” method, the content of the organic polymer component in the chemical conversion treatment layer can be adjusted by the content of the polymer component in the treatment agent.

  In the unpublished German patent application No. 105000050314.3, there is described a “wet in wet” method for the anticorrosion treatment of metal surfaces, where B, An acidic aqueous solution of a fluoride complex of at least one element selected from Si, Ti, Zr and Hf elements is brought into contact with the metal surface. The acidic aqueous solution further contains small amounts of polyallylamine and various metal ions such as copper (II) ions, aromatic carboxylic acids and particulate silica. In this “wet-in-wet” method, a chemical conversion coating layer is produced. This conversion coating layer consists almost entirely of inorganic components and is electrodeposited immediately after processing and without an intermediate drying step.

  In the above-mentioned document, it is clear that the treated metal surface looks like a metallic bright color because the chemical conversion treatment layer produced is colorless and translucent. Known methods for producing a chromium-free colored chemical conversion layer on a metal include organic dyes such as alizarin (International Publication WO 00/26437), fluorescent organic compounds such as stilbene derivatives or coumarin derivatives (US patents). No. 5,516,696), or adding, for example, a transition metal compound of molybdenum (WO 94/25640).

  On the other hand, WO 2005/116294 discloses a treating agent for chemical conversion treatment carried out in the presence of an organic polymer, which firstly enhances the anticorrosive action and Since 2 contains a chromophore substituent, the presence of this polymer on the metal surface can be perceived with the naked eye. Here, the luminescent marker substituent is selected from toluidine blue and neutral red. The advantage of such a treatment agent is that luminescent molecules, ie marker molecules that provide color perception, are permanently attached to the polymer structure. Therefore, since the light emission phenomenon is clearly caused by the presence of the chemical conversion treatment layer, the layer thickness of the chemical conversion coating layer can be estimated as necessary.

  A disadvantage of the above-described method is that the chemical conversion treatment layer, which is an organic-inorganic hybrid layer having a polymer component below a predetermined amount, is not able to be recognized by the naked eye alone because the luminescence phenomenon is significantly reduced. However, in principle, when a high polymer component must be realized in the chemical conversion layer, derivatization of a film-forming polymer having a chromophore or a luminescent marker molecule is often used during synthesis, particularly in the case of “coating / drying processing”. Costly and expensive.

  It has recently been found advantageous to contain particulate inorganic pigments as an additional component in the chemical conversion treatment. Such pigments serve to improve paint adhesion and corrosion resistance to the chemical conversion layer, just like the polymer component, as long as they are present as nanoscale particles. Thus, DE 10161383 discloses a particulate inorganic system selected from compounds of aluminum, barium, cerium, calcium, lanthanum, silicon, titanium, yttrium, zinc or zirconium having an average particle size of 6 to 150 nm, “coating / drying”. It is disclosed as an additional component of an anticorrosive treatment used for layer formation in a "mold" process.

WO 00 / 71626A US 5,516,696 WO 94 / 25640A WO 2005 / 116294A DE 10161383A

European Guidelines 2000/53 / EC European Guidelines 2005/673 / EC

  Accordingly, it is an object of the present invention to produce a coating layer having high corrosion resistance and good paint adhesion in a single step and to emit light (luminesce) when irradiated with ultraviolet light (luminesce). An anticorrosion treatment method is provided. Furthermore, it is desirable that the ratio between the organic content and the inorganic content of the anticorrosion coating layer is adjustable over a wide range, and it is desirable that the intensity of the light emission phenomenon is substantially independent of this ratio.

  The object is to provide an aqueous anticorrosion treatment agent containing at least one particulate inorganic pigment and containing no chromium, and to prevent corrosion of metal surfaces. This is achieved by an aqueous anticorrosive agent that emits light when the pH value of the anticorrosive agent is 1 or more and 4 or less.

  By definition, the treatment solution does not contain chromium, i.e. it does not contain intentionally added chromium compounds. However, it is not possible to exclude a very small amount of chromium as an impurity generated by leaching from the container material, for example.

  “Luminescence” is generally understood by those skilled in the art to mean radiative relaxation of electronically excited atoms, molecules, and / or solid states by the emission of photons. In the present invention, the preferred light emission type is fluorescence and / or phosphorescence generated by irradiation with ultraviolet rays. The wavelength of ultraviolet light typically used according to the present invention to electronically excite particulate inorganic pigments should not be shorter than 200 nm, preferably shorter than 280 nm, particularly preferably shorter than 320 nm. Must not be short. The upper limit of the long wave of excitation radiation (“ultraviolet rays”) is approximately 400 nm, but can also be extended into the visible light region.

  The inorganic luminescent pigment that can be used in the present invention includes a “base material” and at least one doping element. According to the invention, a “matrix” is defined as a material whose elements are partially replaced by a small amount of so-called doping elements. The doping element is different from the element forming the base material.

  The particulate inorganic pigment used in the present invention is at least partially crystalline or has a crystalline domain. In this crystalline domain, the lattice elements (for example, atoms or ions) in the regularly repeating element cell have a stereoregular structure so as to form a three-dimensional lattice. These crystalline domains within the inorganic pigment particles to be used in the present invention form a crystalline basic structure, denoted below as the “main lattice”. By doping this type of main lattice with suitable foreign atoms, light is emitted when irradiated with light of a suitable wavelength. When an individual foreign atom receives light energy, it is converted to an excited electron atomic state and then relaxes back to the electronic ground state by emitting lower energy photons.

It is preferred for the present invention if the matrix of the luminescent pigment is selected from metal or metalloid oxides, sulfides or oxide-sulfides. Here, aluminum (preferably Al ³⁺ ), germanium (preferably Ge ⁴⁺ ), silicon (preferably Si ⁴⁺ ), scandium (preferably Sc ³⁺ ), yttrium (preferably Y ³⁺ ), lanthanum ( Preferably La ³⁺ ), cerium (preferably Ce ³⁺ ), praseodymium (preferably Pr ³⁺ ), neodymium (preferably Nd ³⁺ ), samarium (preferably Sm ³⁺ ), europium (preferably Eu ³⁺ ), Gadolinium (preferably Gd ³⁺ ), terbium (preferably Tb ³⁺ ), dysprosium (preferably Dy ³⁺ ), holmium (preferably Ho ³⁺ ), erbium (preferably Er ³⁺ ), thulium (preferably Is a small member of the group consisting of Tm ³⁺ ), ytterbium (preferably Yb ³⁺ ), or lutetium (preferably Lu ³⁺ ). It is also preferred to select a metal or metalloid from at least one.

Specifically, main lattices derived from the lattice structure of velovskite, such as Mg ₂ GeO ₆ , BaMgAl ₁₀ O ₁₇ , CeMgAl ₁₀ O ₁₉ , and Y ₂ O ₃ , and similar sulfide main lattices or mixed oxides -Sulfide main lattice is preferred.

The matrix is preferably doped with a doping element selected from at least one metal cation of a Group III or Group IV transition metal or rare earth metal of the periodic table. According to the definition of the doping element, it is clear that the metal selected as the doping element is different from the base metal. The doping element comprises at least one metal cation Mn ²⁺ , Mn ⁴⁺ , Ce ³⁺ , Pr ³⁺ , Nd ³⁺ , Sm ³⁺ , Eu ²⁺ , Eu ³⁺ , Gd ³⁺ , Tb ³⁺ , It is still preferred that it is selected from Dy ³⁺ , Ho ³⁺ , Er ³⁺ , Tm ³⁺ , Yb ³⁺ , or Lu ³⁺ .

  In the context of the present invention, such a doped matrix is in the form of particulate inorganic pigments that emit light in the visible light region when irradiated with ultraviolet light, and in particular can be perceived by the human eye, ie sufficient intensity It is particularly preferred that it is in the form of a particulate inorganic pigment that emits light. For this purpose, the light emission characteristics of the pigment itself should be considered, not the light emission characteristics of the treatment agent or concentrate of the present invention.

  In the context of the present invention, particles or particle sizes are classified based on the size of “primary particles”. “Primary particles” are understood to mean particles held together by primary ionic or covalent forces, for example in the form of a crystal lattice. In contrast to primary particles, “secondary particles” consist of two or more primary particles that adhere to each other at the outer surface or grain boundaries of the primary particles by weak ionic forces or other forces based on polarity. It is understood to mean an aggregate. These particles can be split together with low energy consumption, for example by simple mechanical dispersion and / or by addition of a dispersant, thereby eliminating or reducing the weak binding forces present between the primary particles. .

  Effective integration of these particles, or generally good film-forming properties, is a prerequisite for the use of particulate inorganic luminescent pigments as a marker material with good paint adhesion and anti-corrosion properties according to the present invention. . As a result, out of 100 inorganic pigment particles contained in the treatment agent or concentrate according to the present invention, preferably at least 1 particle, preferably at least 10 particles are 2 μm or less, preferably 0.2 μm or less, particularly preferably. The particle size is 0.02 μm or less.

  Basically, any particle measurement method is suitable for measuring the particle size distribution of the pigment particles according to the present invention, and a measurement method based on the optical diffraction principle is preferred. The particle size data presented in the context of the present invention refers to measurements made using a MASTERSIZER X instrument (version 1.2b) from Herrsching, Malvern Instruments, Germany. The operating principle of this device is based on the diffraction of the light beam in that the particle size is related to the diffraction angle. Optical diffraction measurements are instantaneous and can be performed at any time in the treatment agent or concentrate according to the invention.

Another particle size measurement method is, for example, particle size analysis. For particle size analysis, a small amount of a homogeneous suspension of powder to be investigated is prepared in a suitable dispersant and then allowed to settle. Of course, the dispersion treatment agent or concentrate according to the present invention can also be used directly for the purpose of such sedimentation analysis for particle size measurement. From the relationship given by Stoke's law between the size and density of the particles (assuming spheres) and the settling velocity of these particles, draw conclusions over the entire settling process for the particle size distribution Can do. The particle size distribution of the nanoscale dispersion can also be measured by ultracentrifugation. In this ultracentrifugation method, sedimentation can be performed at a maximum gravity of 10 ⁵ times. Other particle size measurement methods include microscopy, electron microscopy, sieve analysis, and surface density measurement.

  Since the treatment agent or concentrate according to the present invention exists mainly as a suspension or dispersion of inorganic pigment, real-time particle size measurement immediately after preparation of the treatment agent or concentrate makes sense. Since the settling and / or flocculation process defines the stability of such a suspension or dispersion, a maximum storage time or maximum processing time is defined for the treatment agent or concentrate according to the invention. Therefore, in order to optimally solve the problems underlying the present invention, continuous measurement process control for the above preferred particle size of the particulate inorganic luminescent pigment in the treating agent or concentrate is required. As a result, at least 50% by weight of the initially added pigment component in the treatment agent or concentrate according to the invention should be present as a suspension and / or dispersion, in which case the inorganic pigment particles are Of the 100 grains, preferably at least 1 grain, preferably at least 10 grains have a grain size of 2 μm or less, preferably 0.2 μm or less, particularly preferably 0.02 μm or less.

上記式中、Ｄ_maxは、この直径Ｄ_max以下の粒子の数画分が測定される際の粒径の上限である。 The percentage number of pigment particle content up to a defined particle size in the dispersion and / or suspension is calculated from the experimentally determined particle size distribution N (D) as follows:

In the above formula, D _max is the upper limit of the particle size when several fractions of particles having a diameter of D _max or less are measured.

  The amount of the particulate inorganic pigment component contained in the treatment agent of the present invention that emits light when irradiated with ultraviolet rays, and specifically forms a composition for the so-called “rinsing method” at the same time is preferably It is 0.05 g / liter or more, particularly preferably 0.5 g / liter or more, and preferably 10 g / liter or less.

The particulate inorganic pigment contained in the treatment agent according to the present invention is deposited on the metal surface from the aqueous phase at a specified pH of 1 to 4 by bringing the surface into contact with the treatment agent. Form. This occurs because the primary particles close to the metal surface suffer from destabilization and aggregation. Such layering destabilization of the dispersed pigment particles itself is caused by an increase in pH at the metal surface caused by corrosive etching of the metal surface. The increase in pH can extend over a few micrometers (10 ⁻⁴ cm) within the treatment solution.

  The corrosion resistance and stability of this coating layer is now that of titanium, zirconium, hafnium, silicon, aluminum, germanium, tin or boron elements that induce the formation of metal surfaces into inorganic layers containing various cations of fluoride complexes. As a result of adding the fluoride complex to the treating agent according to the present invention, a significant improvement can be achieved, with the result that the luminescent pigment is more effectively fixed on the metal surface.

  In particular, the treatment agent of the present invention for simultaneously forming an application solution for the so-called “rinsing method” is preferably 0.01 g / liter or more in total, preferably 0.025 g / liter or more, and 2 g / liter. Liters, preferably 1 g / liter or less, in particular 0.5 g / liter or less of titanium, zirconium, hafnium, silicon, aluminum, germanium, tin or boron elements, and at least a predetermined amount of fluoride, The atomic ratio of Ti and F and / or Zr and F and / or Si and F is 1: 1 to 1: 6. Here, the Ti ion, Zr ion and / or Si ion can be added in the form of a hexafluoride complex such as hexafluoride acid or a water-soluble salt within the above concentration range, such as a sodium salt. In this case, the atomic ratio is 1: 6. However, it is also possible to add a complex compound in which less than 6 fluoride ions are bonded to the central element Ti, Zr or Si, respectively. These complex compounds are naturally formed when at least one of the central elements Ti, Zr or Si and at least one additional compound of one of these central elements is added to this solution. It is possible. Examples of additional compounds include nitrates, carbonates, hydroxides, and / or oxides of the same or different elements of the three central elements.

  In a further embodiment of the invention, in order to allow more efficient binding of the luminescent pigments and to enhance the paint adhesion of the otherwise purely inorganic anticorrosion coating layer, Dispersible and / or water-soluble polymers or polymer blends with similar layering properties can also be included. In this case, when treated with an aqueous polymer-containing agent, an organic-inorganic layer coating is formed on the metal surface. The amount of organic or inorganic components on the layer can be adjusted over a wide range, firstly by the composition of the treatment agent according to the invention and secondly by the deposition method.

  Water-dispersible and / or water-soluble polymers or polymer mixtures can be divided into various groups, notably epoxy resins, aminoplast resins, phenol-aldehyde resins, polymers containing carboxylic acid groups, polymeric alcohols, polymeric alcohols and carboxylic acid groups. Esterification products with polymers containing, polymers containing amino groups, vinylpyrrolidone homopolymers or copolymers, and polymers containing phosphinic acid groups, phosphonic acid groups or phosphate ester groups.

  Specifically, an amino-substituted polyvinylphenol compound obtained as an addition reaction product by a Mannich reaction between polyvinylphenol and an aldehyde and an organic hydroxyl group-containing amine is used as the phenol aldehyde resin. Examples of such poly-4-vinylphenol compounds can be found in WO 00/26437 and references cited in this application, such as specifically US Pat. No. 5,281,282.

Further preferred water-soluble and / or water-dispersible organic polymers are:
a) polyvinyl alcohol, or a water-soluble and / or water-dispersible partial ester thereof,
b) polymers or copolymers of unsaturated monocarboxylic or dicarboxylic acids or their amides,
c) esters of the polymers of groups a) and b),
d) vinylpyrrolidone polymers or copolymers,
e) a polymer of diglycidyl ether of bisphenol A,
f) selected from copolymers of alkylenephosphonic acid or alkylenephosphinic acid and one or more unsaturated carboxylic acids.

  With respect to the polymers of group a), “partial ester” is understood to mean that only some of the alcohol groups are esterified, this ester formation resulting from a non-polymeric carboxylic acid. Specifically, this esterification can be realized with a monobasic carboxylic acid having 1 to 4 carbon atoms.

  The polymer or copolymer of group b) can be selected from homopolymers or copolymers of acrylic acid and / or methacrylic acid. These acid groups can be partially substituted with amide groups or esterified with alcohols, specifically simple alcohols having 1 to 4 carbon atoms. Specific examples are homopolymers and copolymers of or having methyl methacrylate, n-butyl acrylate, hydroxyethyl acrylate and glycerol propoxy triacrylate. Specific examples of these are known, for example, from WO 95/14117. In addition, the polymer of group b) can also be selected from polymers comprising maleic monomers. A specific example in this case is a maleic acid-methyl vinyl ether copolymer.

  The polymers of group a) generally contain free alcohol groups and the polymers of group b) contain free carboxylic acid groups. Thus, both these polymers can not only be added together as a blend, but also in a form in which at least partial esterification of the alcohol groups of polymer a) and the carboxylic acid groups of polymer b) has occurred. You can also. This is discussed in more detail in WO 94/12570. The teachings described can also be applied in the context of the present invention.

  In addition, the treatment solution can comprise a polymer of group d). Such polymers and the use of these polymers in the treatment solution for the chemical conversion treatment are according to DE 100 05 113 and DE-A-101 31 723. It is described in detail.

  Furthermore, the additional polymer can be selected from the polymers of group e) as described in more detail in US Pat. No. 5,356,490.

  The average molecular weight of the organic polymer is preferably at least 10,000 daltons. As long as the polymer is soluble or dispersible within the intended concentration range, preferably in an acidic processing solution, the upper molecular weight limit is not critical. For example, the upper limit of the molecular weight can be 50,000,000, in particular 20,000,000 and specifically preferably 10,000,000 daltons. An upper limit of 5,000,000 daltons may be sufficient. The average molecular weight is preferably greater than 50,000 daltons, especially greater than 100,000 daltons. The average molecular weight can be measured, for example, by gel permeation chromatography using a polyethylene glycol standard.

  In particular, the amount of water-dispersible and / or water-soluble polymer or polymer mixture component in the treatment agent of the present invention, which simultaneously forms a coating solution for the so-called “Rinse-methods”, is 1 ppm or more, Especially preferably, it is 50 ppm or more, and preferably 1000 ppm or less.

  The pH of the treatment agent according to the invention should not be significantly below 1. This is because the etching action on the metal surface becomes stronger as the pH value becomes lower. The pH value is preferably 2 or more, particularly 2.5 or more. When the pH value exceeds 6, the chemical conversion treatment layer and / or the layer-forming precipitate of inorganic luminescent particles are no longer sufficiently produced. This treating agent preferably functions at a pH value of 4 or less, especially 3.5 or less.

  As an optional component that further improves the corrosion resistance and / or paint adhesion of the coating layer resulting from the treatment by the treatment agent of the present invention, the treatment agent of the present invention may contain various auxiliary agents and additives.

These include acid-stable particulate inorganic pigments that do not emit light in the visible light region, preferably silicates, particularly preferably SiO ₂ . The acid-stable particulate inorganic pigment component is 0.05 g / liter or more and 10 g / liter or less.

  Further inorganic compounds in particulate form which can be added to the treatment agent according to the invention are particularly preferably carbonate compounds, oxides, silicates or sulfates, in particular aluminum, barium, cerium, calcium, lanthanum, silicon, titanium, yttrium. Colloidal or amorphous particles based on zinc and / or zirconium, in particular aluminum oxide, barium sulfate, cerium dioxide, rare earth mixed oxide, silicon dioxide, silicate, titanium oxide, yttrium oxide, zinc oxide, and / Or zirconium oxide.

  The acid-stable particulate inorganic pigment that does not emit light when irradiated with ultraviolet rays has a particle size of at least 1 particle, preferably at least 10 particles out of 100 acid-stable inorganic pigment particles, preferably 2 μm. It has a particle size distribution such that it does not exceed 2 μm, particularly preferably 0.02 μm. Higher than inorganic pigments when a substrate treated or coated according to the invention, in particular a substrate with a high polymer component content, is intended to be welded in a layer coating with a layer thickness of more than 1 μm Or compounds in the form of particles having the same conductivity, specifically oxides, phosphates, phosphides or sulfides of aluminum, iron or molybdenum, in particular aluminum phosphide or iron oxide, phosphide It may be advantageous to incorporate iron, at least one molybdenum compound, such as molybdenum sulfide, graphite, and / or carbon black. These particles can also have an average particle size, optionally protruding somewhat from the layer produced according to the invention.

  Furthermore, the treatment agent of the present invention may additionally contain a copper cation and / or molybdenum, tungsten and / or vanadium oxoanion in an amount of 5 ppm to 200 ppm.

  The treating agent of the present invention may contain a phosphorus oxoanion, preferably a phosphate anion, in terms of elemental phosphorus, with an oxoanion content of 0.5 g / liter or more and 20 g / liter or less.

  In order to increase the etching rate for the surface to be treated, which is at least partly composed of aluminum, and thus to accelerate the deposition of the conversion treatment layer and / or the inorganic substances, the treatment agent according to the invention further comprises fluoride ions. be able to. The fraction of fluoride ions is 0.05 g / liter or more and 5 g / liter or less.

“Accelerators” derived from the field of anticorrosive phosphate treatment known to those skilled in the art that increase the etching attack on the metal substrate can be used to deposit a homogeneous film. Accordingly, the treating agent according to the present invention may comprise at least one of the following “accelerators”:
0.3 to 4 g / liter chlorate ion,
0.01 to 0.2 g / liter nitrite ion,
0.05 to 4 g / liter nitroguanidine,
0.05 to 4 g / liter N-methylmorpholine-N-oxide,
0.2 to 2 g / liter m-nitrobenzenesulfonate ion,
0.05 to 2 g / liter m-nitrobenzoate ion,
0.05 to 2 g / liter p-nitrophenol,
1 to 150 mg / liter hydrogen peroxide in free or bound form,
0.1 to 10 g / l hydroxylamine in free or bound form,
0.1 to 10 g / liter reducing sugar

  A further aspect of the present invention provides a concentrate that, when suitably diluted, results in the treatment agent of the present invention or that can be used directly as a concentrated aqueous composition for deposition, ie for treating metal surfaces. It is to provide. Such direct use of the concentrate according to the invention is particularly suitable for so-called “non-rinse” processes. In this “non-rinse” method, a defined liquid film is deposited on a metal substrate (eg by roller deposition or spraying by squeezing) and subsequently dried to form a layer. These types of “non-rinse” concentrates have a high content of water-soluble and / or water-dispersible polymers that form a homogeneous film at a suitable specific temperature (“film formation temperature”). is doing.

  Accordingly, the present invention includes an aqueous concentrate for anticorrosion treatment of metal surfaces, and when diluted with water by 10 times or more and 200 times or less, the concentrate provides the treatment agent of the present invention according to the above preferred composition.

Preferably, the concentrate is diluted by a factor of 10 to 200 times,
a) Titanium, zirconium having a total content of 0.01 g / liter or more, preferably 0.025 g / liter or more and 2 g / liter or less, preferably 1 g / liter or less, particularly 0.5 g / liter or less, Fluoride complexes of hafnium, silicon, aluminum, germanium, tin or boron elements;
b) at least one dispersible and / or water-soluble polymer having a fraction of 1 ppm or more, particularly preferably 50 ppm or more and preferably 1000 ppm or less; or c) both a) and b) In the concentrate, the particulate inorganic pigment that emits light when irradiated with ultraviolet rays is 0.05 g / liter or more, particularly preferably 0.5 g / liter or more. And preferably at a content of 10 g / liter or less.

When the present invention is also diluted only by a multiple of 10 to 200 times,
a) a particulate inorganic pigment having a content of 0.05 g / liter or more, particularly preferably 0.5 g / liter or more, and preferably 10 g / liter or less, which emits light when irradiated with ultraviolet light;
b) the present invention comprising at least one water-dispersible and / or water-soluble polymer having a content of 1 ppm or more, particularly preferably 50 ppm or more and preferably 1000 ppm or less; or c) both a) and b) A concentrate which provides any of the treatment agents in which the fluoride complexes of titanium, zirconium, hafnium, silicon, aluminum, germanium, tin or boron elements total 0.01 g / It is contained in a content of not less than liter, preferably not less than 0.025 g / liter and not more than 2 g / liter, preferably not more than 1 g / liter, particularly not more than 0.5 g / liter.

When the present invention is further diluted 10 times or more and 200 times or less,
a) a particulate inorganic pigment that emits light when irradiated with ultraviolet light in an amount of 0.05 g / liter or more, particularly preferably 0.5 g / liter or more, and preferably 10 g / liter or less;
b) at least one water-dispersible and / or water-soluble polymer with a content of 1 ppm or more, particularly preferably 50 ppm or more and preferably 1000 ppm or less; and c) a total of 0.01 g / l or more, preferably 0 0.025 g / liter or more and 2 g / liter or less, preferably 1 g / liter or less, particularly 0.5 g / liter or less of titanium, zirconium, hafnium, silicon, aluminum, germanium, tin or boron element. Including a concentrate resulting in a treating agent of the present invention comprising a fluoride complex;
One or more optional ingredients as described above are included in the concentrate in a suitable and preferred amount.

  Furthermore, the concentrate according to the present invention is substantially free of a chromium compound, and the content of the chromium compound is preferably less than 100 ppm in terms of elemental chromium.

  Furthermore, the pH value of the concentrate according to the present invention is 1 or more and 4 or less when diluted with a multiple of 10 to 200 times. Thus, the pH value of the concentrate may be less than 1, but not less than 0.3.

  The method according to the invention comprises the steps of treating a metal surface with such a treatment agent, and a metal surface resulting from an inorganic pigment according to the invention impregnated and / or surface-immobilized in a protective layer prior to corrosion of the metal layer. Optically assessing the quality of the process by making the emission of the material as uniform as possible and additional steps derived from these steps to optimize the process and / or coating layer quality Steps.

  Accordingly, the present invention also includes a metal substrate that has been treated according to one or more of the above methods (“rinse” method / “no rinse” method), and the substrate thus treated comprises: It emits light when irradiated with ultraviolet light, and preferably this light emission can be observed in the visible light region.

  The metal substrate thus treated or coated can be used for car body assembly, ship construction, construction industry, and white (large) home appliance manufacturing in automobile manufacturing.

  The metal surface that can be treated with the treating agent, concentrate and method of the present invention is preferably zinc and zinc alloy, galvanized steel or alloy plated steel, aluminum and aluminum alloy, magnesium and magnesium alloy, titanium and titanium Selected from alloys. The metal surface may be the surface of the metal or the alloy itself, but may also be the surface of a substrate such as steel plated with the metal or the alloy thereof. Examples of the latter are electroplated steel, or coated steel such as Galvalume® or Galfan® with a coating of hot dip galvanized steel, aluminized steel, or zinc / aluminum alloy.

Claims (34)

  An aqueous anticorrosive treatment agent comprising at least one inorganic pigment, wherein the particulate inorganic pigment emits light when irradiated with ultraviolet rays and has a pH value of 1 or more and 4 or less, and is used for corrosion protection of metal surfaces. Aqueous anticorrosive treatment agent for treatment.   The aqueous anticorrosive treatment agent according to claim 1, further comprising at least one of a fluoride complex of titanium, zirconium, hafnium, silicon, aluminum, germanium, tin, or boron element.   The aqueous anticorrosive treatment agent according to claim 1, further comprising at least one water-dispersible and / or water-soluble polymer.   2. Further comprising at least one of a fluoride complex of titanium, zirconium, hafnium, silicon, aluminum, germanium, tin or boron element and at least one of a water dispersible and / or water soluble polymer. The aqueous anticorrosive treatment agent according to any one of -3.   5. The main lattice structure type inorganic compound doped with one or more of a group III or group IV transition metal or rare earth metal cation of the periodic table in the particulate pigment. The aqueous anticorrosive treatment agent according to claim 1.   The aqueous anticorrosive treatment agent according to claim 5, wherein a main lattice structure of the particulate inorganic pigment is composed of an oxide.   The aqueous anticorrosive treatment agent according to any one of claims 1 to 6, wherein the particulate inorganic pigment emits light to a perceptible level in a human visible light region.   At least 1/100, preferably at least 10/100, of the inorganic pigment contained comprises a particle size of 2 μm or less, preferably 0.2 μm or less, more preferably 0.02 μm or less. 8. The aqueous anticorrosive treatment agent according to any one of 7 above.   The aqueous anticorrosion according to any one of claims 3 to 8, wherein an addition reaction product by a Mannich reaction between polyvinylphenol and an aldehyde and an organic hydroxyl group-containing amine is used as the water-dispersible and / or water-soluble polymer. Processing agent.   The water-dispersible and / or water-soluble polymer is selected from polymers of polyvinyl alcohol, bisphenol A-diglycidyl ether, and / or polymers and copolymers of acrylic acid, methacrylic acid and maleic acid and esters or amides of these acids. The aqueous anticorrosive treatment agent according to any one of claims 3 to 9.   The aqueous anticorrosive treatment agent according to any one of claims 3 to 10, wherein the content of the water-dispersible and / or water-soluble polymer is 1 ppm or more and 1000 ppm or less.   The aqueous anticorrosive treatment agent according to any one of claims 1 to 11, wherein the content of the particulate inorganic pigment that emits light upon irradiation with ultraviolet rays is 0.05 g / liter or more and 10 g / liter or less.   The content of the fluoride complex of the titanium, zirconium, hafnium, silicon, aluminum, germanium, tin, or boron element is 0.1 g / liter or more and 2 g / liter or less, any one of claims 2 and 4 to 11 The aqueous anticorrosive treatment agent according to Item 1. It further comprises one or more acid-stable particulate inorganic pigments that do not emit light in the visible light region, wherein the acid-stable particulate inorganic pigment is preferably silicate, more preferably SiO ₂ , and the acid stable The aqueous anticorrosive treatment agent according to any one of claims 1 to 13, wherein a content of the fine particulate inorganic pigment is 0.05 g / liter or more and 10 g / liter or less.   The aqueous anticorrosive treatment agent according to any one of claims 1 to 14, further comprising a copper cation and / or molybdenum, tungsten and / or vanadium oxoanion in a content of 5 ppm to 200 ppm.   The phosphorus oxoanion, preferably a phosphate anion, is further contained in a content of 0.5 g / liter to 20 g / liter in terms of phosphorus element. An aqueous anticorrosive treatment agent.   The aqueous anticorrosive treatment agent according to any one of claims 1 to 16, further comprising fluoride ions at a content of 0.05 g / liter or more and 5 g / liter or less.   Selected from nitroguanidine, N-methylmorpholine-N-oxide, m-nitrobenzenesulfonate ion, m-nitrobenzoate ion, p-nitrophenol, hydroxylamine, hydrogen peroxide, nitrite ion, and / or reducing sugar The aqueous anticorrosive treatment agent according to claim 1, further comprising a reaction accelerator.   The aqueous anticorrosive agent according to any one of claims 1 to 18, which is substantially free of a chromium compound, and preferably has a chromium compound content of less than 100 ppm in terms of elemental chromium.   An aqueous concentrate for anticorrosion treatment of a metal surface, wherein the aqueous anticorrosion treatment agent according to any one of claims 2 to 18 is obtained by diluting with water to 10 to 200 times.   The concentrated liquid according to claim 20, further comprising a particulate inorganic pigment that emits light upon irradiation with ultraviolet rays, as described in claim 12.   The concentrate according to claim 20 or 21, further comprising a fluoride complex of titanium, zirconium, hafnium, silicon, aluminum, germanium, tin, or boron element according to claim 13.   The concentrated solution according to any one of claims 20 to 22, further comprising at least one component according to any one of claims 14 to 22.   The concentrated solution according to any one of claims 20 to 23, which is substantially free of a chromium compound and preferably has a chromium compound content of less than 100 ppm in terms of elemental chromium.   The concentrated solution according to any one of claims 21 to 24, wherein the pH value is 4 or less and 0.3 or more.   An anticorrosion treatment method for a metal surface, comprising bringing the cleaned metal surface into contact with the aqueous anticorrosion treatment agent according to any one of claims 1 to 25 or a concentrated liquid thereof.   After the cleaned metal surface is brought into contact with the aqueous anticorrosive treatment agent according to any one of claims 1 to 25 or a concentrated liquid thereof, the aqueous coating layer adhered to the metal surface is dried, thereby 27. A method according to claim 26, wherein the thickness of the coating layer formed after drying is 5 [mu] m or less, preferably 1 [mu] m or less, but at least 0.02 [mu] m.   Immediately after contacting the metal surface with the aqueous anticorrosive treatment agent according to any one of claims 1 to 19, without an intermediate drying step, followed by an additional cleaning step, a post-treatment step and / or a coating step. 27. The method of claim 26, wherein:   28. The method according to claim 27, wherein an additional washing step, a post-treatment step and / or a coating step are performed. The metal surface treated by the above step is subjected to ultraviolet irradiation with or without an intermediate cleaning step, optically evaluated for the uniformity of the light emission phenomenon on the entire surface of the treated metal surface, and light emission is not caused. If homogeneous, the following:
(A) The method of claim 26 or 27 is repeated until the light emission when irradiated with ultraviolet rays is as homogeneous as possible on the entire surface of the metal surface,
(B) A part of the metal surface that does not emit light at all or a part that has a very low evaluation value of light emission compared to the entire metal surface is partially treated by the method according to claim 26 or 27, Repeating the treatment until the entire surface of the metal surface is as uniform as possible when irradiated with ultraviolet light;
(C) adjusting at least one parameter that causes cleaning of the metal surface such that the additional treatment of the metal surface of claim 26 or 27 is such that the luminescence phenomenon of the entire surface of the treated metal surface is as homogeneous as possible. ,
(D) By increasing the amount of at least one component of the aqueous anticorrosive treatment agent according to at least one of claims 1 to 25 or a concentrated solution thereof, the amount of each component specified in claims 1 to 25 is The additional treatment of the metal surface according to the method of claim 26 or 27 is performed so that the light emission phenomenon on the entire surface of the treated metal surface is as uniform as possible so that there is no excess and no shortage. Or (E) applying post-passivation of the entire surface of the metal surface in a subsequent step;
28. The method of claim 26 or 27, wherein:   31. The method according to claim 30, wherein both the optical evaluation of the luminescence phenomenon and the processing steps (AE) performed as a result are performed automatically without human intervention.   32. A metal substrate treated by the method according to claim 26, wherein the metal substrate treated by the method emits light upon irradiation with ultraviolet rays.   The metal substrate according to claim 32, wherein the emitted light is observed in a visible light region by a human eye.   34. Use of a metal substrate according to claim 32 or 33 in car body assembly, ship construction, assembly industry and white goods (large sized) home appliance manufacture in automobile manufacture.