KR100609482B1 - Conditioning liquid and conditioning process used in pretreatment for formation of phosphate layer on the metallic surface - Google Patents

Abstract

A new adjustment liquid is provided for use in pretreatment prior to forming the phosphate layer, which is suitable for effectively producing a finely crystallized phosphate layer and whose long term excellent properties are maintained.

The adjustment liquid of the present invention contains phosphate particles of divalent and / or trivalent metals and also contains an accelerating component. As an accelerating component, a saccharide, a phosphate compound, a polymer of vinyl acetate, and a specific aqueous high molecular compound are preferable. The size of the phosphate particles is preferably less than 5 μm. The concentration of the accelerating component is preferably 1 to 2000 ppm. Prior to forming the phosphate layer, the metal surface is contacted with the adjusting liquid. A washing | cleaning effect can also be provided to an adjustment liquid.

Phosphate layer, metal surface treatment, adjustment liquid

Description

Conditioning liquid used in pretreatment prior to forming phosphate layer on metal surface and method of adjustment {CONDITIONING LIQUID AND CONDITIONING PROCESS USED IN PRETREATMENT FOR FORMATION OF PHOSPHATE LAYER ON THE METALLIC SURFACE}

The present invention is for surface adjustment before chemically forming a phosphate layer on a metal surface, which is applied to steel, galvanized steel, aluminum and magnesium alloys to accelerate and accelerate the chemical reaction in the phosphate layer and to produce fine phosphate crystals. A process liquid and a surface adjustment process.

Recently, it has been required to form fine and dense phosphate crystals in the phosphate layer in order to improve the corrosion resistance after painting and to reduce the friction during the cooling operation of the metal. Thus, in recent years, surface conditioning processes are often performed prior to chemically forming the phosphate layer to activate the metal surface and make nuclei suitable for producing fine and dense phosphate crystals. Conventional processes for obtaining fine dense phosphate crystals are illustrated below. The phosphate layer is prepared in the next step.

(1) Grease Removal

(2) washing (multilevel)

(3) surface adjustment

(4) chemical formation of the phosphate layer

(5) defensive (multilevel)

(6) Rinse with pure water.

Surface conditioning processes are employed to make the phosphate crystals fine and dense. Commonly used chemical complexes are described in US Pat. Nos. 2874081, 2322349, 2310239, and the like, and disclosed are adjustment solutions containing titanium, pyrophosphate ions, orthophosphate ions, sodium ions, and the like. This complex is called Jernsteadt salt and the aqueous solution of the complex contains titanium ions and titanium colloids.

When the metal is immersed in the above-mentioned adjusting liquid or sprayed with the solution, titanium colloid is adsorbed on the metal surface. Adsorbed titanium colloids become nuclei in the chemical formation of the phosphate layer, promoting chemical reactions and producing fine and dense crystals. Currently, all industrially used surface control composites use Jernsteadt salts. However, industrially, there are various problems in using Jernstedt salt.

The first problem is that the surface adjustment liquid decomposes over time. When applied with conventional surface modifiers, it has a remarkable effect on making the phosphate crystals fine and dense immediately after preparation of the aqueous solution, but after several days of preparation, the effect is lost, whether used or not, resulting in coarse You lose. This is because the titanium colloid in this adjustment liquid aggregates.

For this reason, JP63-76883A discloses a process of constantly discarding a part of the surface adjustment liquid and adding a new surface adjustment liquid while periodically measuring this to keep the average diameter of the titanium colloid sufficiently small. Although it is possible to quantitatively control the surface adjustment liquid by this method, part of the surface adjustment liquid must be discarded to maintain the effect. Therefore, this method requires a large amount of surface adjustment liquid to be discarded and a large amount of water waste plant is required.

As a second problem, it is mentioned that the effect and the lifetime of the surface modifier are largely dependent on the water quality used for its preparation. In general, tap water is used to prepare the surface adjustment liquid. However, as is well known, tap water usually contains cations such as calcium and magnesium, and the amount of cations varies depending on the water source. Titanium colloids, on the other hand, are known to be charged with anions and remain dispersed without being precipitated by electrical repulsive forces. Thus, when the tap water contains an excess of cationic components, the titanium colloid is neutralized by the cationic component, aggregates and precipitates and loses its repulsive force.

In order to block the cation component and keep the titanium colloid stable, a method of adding a concentrated phosphate such as pyrophosphate to the surface control solution has been proposed. However, excessive addition of concentrated phosphate to the crude liquid results in the formation of an inert coating by the reaction between the concentrated phosphoric acid and the metal surface in the crude liquid, which causes problems in chemically forming the phosphate layer on the metal surface in subsequent subsequent processing steps. . In addition, where tap water contains an excessive amount of calcium or magnesium, pure water must be used to prepare the adjustment liquid, which is economically disadvantageous.

The third problem is the temperature and pH of the application. For example, titanium colloids agglomerate at high temperatures in excess of 35 ° C. and outside the pH 8.0 to 9.5 range and lose surface adjustment effects. Therefore, conventional surface conditioners must be used within a narrow temperature range and a narrow pH range. Therefore, as one kind of liquid, the cleaning effect cannot be given to the surface adjustment liquid.

The fourth problem is that there is a limit to minimizing phosphate crystals. Minimization of phosphate crystals is due to nucleation of titanium colloids adsorbed on metal surfaces to aid in fine phosphate crystallization. Therefore, the finer and denser phosphate crystals can be obtained by adsorbing titanium colloid more on the metal surface.

In order to solve this problem, it is easily proposed to increase the number of titanium colloids in the adjustment liquid. However, the higher the density, the more likely the titanium colloids will collide with each other in the coarse liquor and the better the coagulation and settling. At present, the upper limit for the use of titanium colloids is less than 100 ppm and it is not possible to use a calibration liquid containing titanium colloids at higher densities.

JP-56-156778A and JP57-23066A disclose blast suspensions containing insoluble phosphates of divalent or trivalent metals on steel surfaces under pressure. In this case, however, the effect can only be seen if the suspension is blasted under pressure, and this method is not applicable to the conventional adjustment process of dipping or spraying the metal with the adjustment liquid.

JP40-1095B2 discloses another surface adjustment method of immersing a galvanized steel sheet in a suspension of insoluble phosphate of divalent or trivalent metal. However, applications of this method are limited to those applied to galvanized steel and require the use of high density insoluble phosphates of at least 30 g / L.

As mentioned above, there are already too many problems with the method associated with the Jernstedt salt. However, no technology has yet been used to replace the Jernstedt method.

It is an object of the present invention to solve the above-mentioned problems with the prior art, to promote and accelerate chemical reactions, to produce finer phosphate crystals, and to provide new adjustment liquids and new adjustment processes that are stable over a long period of time.

The present inventors have intensively researched to solve the above problems, and have succeeded in developing a new surface control liquid and a method for adjusting the quality of the phosphate layer.

That is, the present invention is characterized by (1) containing at least one phosphate particle of divalent and / or trivalent metal, and at least one accelerating component selected from monosaccharides, polysaccharides and derivatives thereof. And a control liquid used for pretreatment before forming a phosphate layer on the metal surface.

In addition, the present invention is characterized by (2) containing at least one phosphate particles of divalent and / or trivalent metals, and at least one facilitating component selected from orthophosphates, polyphosphates and organic phosphonic acid compounds. The adjustment liquid used for the pretreatment before forming a phosphate layer.

The present invention also relates to (3) at least one soluble phosphate particles of one or more divalent and / or trivalent metals, and a water-soluble polymer compound selected from polymers of vinyl acetate, derivatives thereof, and copolymers of vinyl acetate with other monomers as accelerating components. It is related with the adjustment liquid used for the pretreatment before forming a phosphate layer on the metal surface characterized by containing.

The present invention also relates to (4) at least one facilitating component selected from one or more divalent and / or trivalent metal phosphate particles and a copolymer or polymer obtained by polymerizing the next monomer i) with less than 50% by weight of the next monomer ii). A control liquid used for pretreatment prior to forming a phosphate layer on a metal surface, characterized in that it contains:

Monomer i) A monomer selected from monomers having the following formula (1) or α-, β-unsaturated carboxylic acid monomers.

(Wherein R ¹ : H or CH ₃ , R ² : H or C _1-5 alkyl group or C _1-5 hydroxyalkyl group)

Monomer ii) Monomer copolymerizable with monomer i).

In the above (1) to (4), the phosphate particles are preferably particles having a diameter of less than 5 μm and the total concentration thereof is preferably 0.001 to 30 g / L, and the divalent or trivalent metal is Zn, Fe, Mn, Ni. At least one selected from Co, Ca, and Al. The total concentration of the facilitating component is preferably 1 to 2000 ppm.

In addition, the adjusting liquid may further contain an alkali metal salt or an ammonium salt or a mixture thereof. These alkali metal salts or ammonium salts are preferably orthophosphates, metaphosphates, orthosilicates, metasilicates, carbonates, bicarbonates, nitrates, nitrites, sulfates, borates and organic acid salts, and the total concentration is preferably 0.5 to 20 g / L. .

The adjusting method of the present invention is to contact the metal surface with the adjusting liquid before forming the phosphate layer.

The adjusting liquid of the present invention is very stable in the high pH range and high temperature as compared with the titanium colloid of the prior art. Thus, the adjustment liquid of the present invention may further contain one or more additives selected from alkali builders and nonionic surfactants and anionic surfactants. In addition, this kind of adjustment liquid of the present invention may have a cleaning effect on the metal surface as a side effect. Therefore, the metal treated with the adjustment liquid of the present invention has a property that is suitable for forming a phosphate layer and a clean surface.

As described above, in the conventional process, three steps of (1) degreasing, (2) washing and (3) surface adjustment had to be performed before the chemical formation step of the phosphate layer. By using the adjustment liquid of the present invention having both the cleaning (grease removal) effect and the surface adjustment effect, the above three steps can be simplified to a one-step process in which grease removal and surface adjustment are combined as described in (1) below. have. That is, two steps can be reduced.

The adjusting liquid of the present invention can effectively provide a surface suitable for forming the phosphate layer in a wider pH range than the pH range according to the prior art. Therefore, in the case of the present invention, it is possible to additionally add an alkali metal salt into the adjustment liquid, and an adjustment liquid having a combination of a washing effect and a surface adjustment effect can be obtained.

(1) Merging process of grease removal and surface adjustment

(2) chemical formation of the phosphate layer

(3) washing (multilevel)

(4) rinse with pure water

Best mode for carrying out the invention

Phosphate particles and accelerating components of divalent or trivalent metals are essential components of the present invention. As described above, an object of the present invention is to produce a nucleus for precipitating phosphate crystals by providing a surface adjustment liquid for activating the metal layer before forming the phosphate layer. The inventors have found that phosphate particles of divalent or trivalent metals of the desired content, having the desired diameter, are adsorbed on the surface of the metal to be treated with the facilitating component in an aqueous solution, creating nuclei for crystallization of the phosphate layer and accelerating the formation of the phosphate layer. It was found to contribute.

Phosphate particles of the divalent or trivalent metal of the present invention are solid and insoluble. However, chemically they are similar to the components of the chemicals used to form the phosphate layer and they are chemically similar to the phosphate layer formed. In addition, they do not adversely affect the phosphate layer forming solution, but also do not adversely affect the phosphate layer even when a part of the adjusting solution flows into the next stage bath containing the phosphate layer forming solution. Examples of the phosphate particles of the divalent or trivalent metal of the present invention include the following.

Zn ₃ (PO ₄ ) ₂ , Zn ₂ Fe (PO ₄ ) ₂ , Zn ₂ Ni (PO ₄ ) ₂ , Ni ₃ (PO ₄ ) ₂ , Zn ₂ Mn (PO ₄ ) ₂ , Mn ₃ (PO ₄ ) ₂ , Mn ₂ Fe (PO ₄ ) ₂ , Ca ₃ (PO ₄ ) ₂ , Zn ₂ Ca (PO ₄ ) ₂ , FePO ₄ , AlPO ₄ , CoPO ₄ , Co ₃ (PO ₄ ) ₂ , and hydrates thereof.

The particle size of the crystals of the phosphate layer gradually decreases as the number of crystals initiating the reaction increases. This is because crystal growth stops when neighboring crystals come into contact with each other. Also, the greater the number of crystals at the start of the reaction, the closer the crystals are to each other and the metal surface is covered in a shorter time with fewer crystals. Therefore, in order to precipitate fine phosphate crystals in a short time, it is advantageous to make more nuclei before the phosphate layer is formed.

The particle size of the divalent or trivalent metal phosphate of the present invention is preferably less than 5 μm in order to stably disperse in an aqueous solution. Even if there are phosphate particles of divalent or trivalent metal having a diameter of more than 5 μm in the adjustment liquid of the present invention, the effect of the present invention is as long as the liquid contains a sufficient amount of phosphate having a particle size of less than 5 μm. Will not be greatly disturbed.

Phosphate particles of divalent or trivalent metals according to the invention also have the effect of promoting precipitation itself. That is, the phosphate particles of the divalent or trivalent metal are absorbed by the metal surface during the adjustment process and some of them are dissolved by themselves during the phosphate layer forming bath in the next step to supply the phosphate component to the phosphate layer near the metal surface, It greatly promotes precipitation of the phosphate layer.

The total amount of phosphate particles of divalent or trivalent metal is preferably in the range of 0.001 to 30 g / L. If the total amount of phosphate particles of the divalent or trivalent metal is less than 0.001 g / L, the amount of phosphate particles of the divalent or trivalent metal adsorbed on the metal surface decreases, which does not promote the initial precipitation of phosphate crystals, Particles do not promote chemical reactions.

It is only uneconomical that the amount of phosphate particles of divalent or trivalent metals exceeds 30 g / L, which does not further enhance phosphate formation.

The promoting components to be contained in the adjustment liquid of the present invention are described below.

As mentioned above, in the prior art, insoluble phosphates of divalent or trivalent metals are blasted under pressure upon surface adjustment. The reason for blasting under pressure is to react by hard hitting insoluble phosphate on the metal surface or to make the metal surface like shot peening. In addition, in order to obtain the surface adjustment effect by the conventional method, the insoluble phosphate density of the divalent or trivalent metal had to be extremely increased.

The inventors of the present invention have found that in the presence of the facilitation component of the present invention, the phosphate particles of divalent or trivalent metals are low density and the surface adjustment effect can be exerted without physically blasting them onto the metal surface. Therefore, in the present invention, it is sufficient to simply contact the metal surface with the adjusting liquid.

The facilitating component of the present invention (hereinafter abbreviated as accelerator) improves the dispersion stability of phosphate particles of divalent or trivalent metal and promotes adsorption of phosphate particles of divalent or trivalent metal on the metal surface. The accelerator of the present invention is adsorbed on the surface of each phosphate particle of divalent or trivalent metal to impart repulsion and solid hindrance effect of charge to the phosphate particles to prevent aggregation and sedimentation of the phosphate particles. Phosphate particles of the valent or trivalent metal interfere with causing mutual collisions. These accelerators also have the ability to adsorb on the metal surface itself, thus adsorbing on the surface of the phosphate particles to promote the adsorption of the phosphate particles on the metal surface. Only by contacting the metal with the adjusting liquid, such adjusting effect can be obtained.

The amount of accelerator is preferably 1 to 2000 ppm. If it is less than 1 ppm, the surface adjustment liquid cannot exert the surface adjustment effect. In addition, the fact that this amount exceeds 2000 ppm does not further improve the effect, and only increases the risk of the metal surface being covered with a promoter, which may make it difficult to adsorb phosphate particles on the metal surface.

The adjusting liquid of (1) of the present invention contains an accelerator selected from monosaccharides, polysaccharides and derivatives thereof. The basic saccharide components of monosaccharides, polysaccharides and derivatives thereof can be selected from: fructose, tagatose, psicose, sulfose, erythrul Erythrulose, trehalose, ribose, arabinose, xylose, lichetose, allose, altlose, glycose , Mannose, gulose, idose, galactose, talos and the like.

Thus, when using monosaccharides, the basic saccharides can be used. If polysaccharide is to be used, homo-polysaccharide or hetero-polysaccharide may be used. If derivatives thereof are also available, they are obtained by esterifying the hydroxyl group of the basic saccharide with a substituent such as, for example, NO ₂ , CH ₃ , C ₂ H ₄ OH, CH ₂ CH (OH) CH ₃ , CH ₂ COOH, or the like. Homosaccharides and heterosaccharides containing monosaccharides or monosaccharides obtained by substitution with the above substituents can be exemplified as derivatives. Combinations of monosaccharides, polysaccharides and derivatives thereof can also be used.

The saccharides can be classified into mono-saccharides, minor-saccharides and poly-saccharides by their hydrolysis. In the present invention it is classified into polysaccharides which produce more than two monosaccharides by hydrolysis and monosaccharides which can no longer be hydrolyzed.

Since the present invention has nothing to do with biochemical reactions, this effect does not depend on the three-dimensional structure or optical rotation of the basic saccharide component, and D-monosaccharides, L-monosaccharides and any optical rotation ( You can use both + and-). In addition, in order to increase the water solubility, the sodium salt and ammonium salt of the monosaccharide, polysaccharide and derivatives thereof can be used without any problem. In addition, if there are difficulties with regard to solubility, these may be dissolved in advance in an organic solvent.

The adjusting liquid of (2) of the present invention contains at least one promoting component selected from orthophosphoric acid, polyphosphoric acid or organic phosphonic acid. As the polyphosphoric acid, pyrophosphoric acid, triphosphoric acid, trimethic acid, tetramethic acid, hexamethic acid and its sodium and ammonium salts can be used. As the organic phosphonic acid, aminotrimethylene phosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetramethylenephosphonic acid, diethylenetriaminepentamethylene phosphonic acid, and its sodium salt can be used. have. In addition, the orthophosphoric acid, polyphosphoric acid and organophosphonic acid can be used alone or in combination without any problem.

The adjustment liquid of (3) of this invention contains at least 1 sort (s) chosen from the aqueous polymer of vinyl acetate, its derivative (s), and the copolymer of the vinyl acetate and the monomer copolymerizable with vinyl acetate as an accelerating component. As a polymer of vinyl acetate and its derivatives, cyanoethylated-polyvinyl alcohol and polyvinyl alcohol obtained by cyanoethylation of polyvinyl alcohol using polyvinyl alcohol and acrylonitrile as a vinyl acetate polymer soap are acetal with formalin. Formalized polyvinyl alcohol obtained by the formation of a polyvinyl alcohol, urethane-polyvinyl alcohol obtained by urethane forming a polyvinyl alcohol, and an aqueous macromolecule obtained by introducing a carboxyl group, a sulfone group, and an amide group into a polyvinyl alcohol. The compound can be mentioned. As the monomer, those copolymerizable with vinyl acetate, acrylic acid, crotonic acid, maleic anhydride and the like can be used.

The polymer of the vinyl acetate or the derivative thereof or the copolymer of the vinyl acetate and the monomer copolymerizable with vinyl acetate exhibits sufficient effects in the present invention as long as it has an aqueous characteristic. This effect is not affected by the degree of polymerization or the degree of introduction of the functional groups, and the monomers or copolymers may be used alone or in combination together without any problem.

The adjusting liquid of (4) of the present invention contains at least one accelerating component selected from copolymers or polymers obtained by polymerization of the following monomers i) and less than 50% by weight of monomers ii).

Monomer i) A monomer selected from monomers having the following formula (1) or α-, β-unsaturated carboxylic acid monomers.

Formula 1

(Wherein R ¹ : H or CH ₃ , R ² : H or C _1-5 alkyl group or C _1-5 hydroxyalkyl group)

Monomer ii) Monomer copolymerizable with monomer i).

As the monomer of Formula 1, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate , Hydroxymethyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxypentyl acrylate, hydroxymethyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate Latex, hydroxybutyl methacrylate, hydroxypentyl methacrylate can be used. Moreover, acrylic acid, methacrylic acid, maleic acid can be used as an (alpha)-, (beta)-unsaturated carboxylic acid monomer. As the monomer ii), vinyl acetate, styrene, vinyl chloride, vinylsulfonic acid can be used. Polymers obtained by polymerizing one of these monomers and copolymers obtained by combining some of these monomers may be used without any problem.

The adjusting liquid of the present invention may contain an alkali metal salt or an ammonium salt or a combination of the two salts. Alkali metal salts and ammonium salts include orthophosphates, metaphosphates, orthosilicates, metasilicates, carbonates, bicarbonates, nitrates, nitrites, sulfates, borates and organic acid salts. It is also possible to use two or more salts in combination without any problem.

Alkali metal salts and ammonium salts used in the present invention may be used as alkali builders and may have the same effects as those contained in industrial cleaners. They impart a softening effect and a grease removal effect to the adjustment liquid, enhance the liquid stability of the adjustment liquid, and also impart a cleaning effect.

The amount of alkali metal salt or ammonium salt is preferably 0.5 to 20 g / L. If it is less than 0.5 g / L, the softening effect and the cleaning effect are insufficient, and if it exceeds 20 g / L, it is only uneconomical.

Unlike the conventional liquid, the adjustment liquid of the present invention can maintain many kinds of effects in the environment. That is, the adjustment liquid of the present invention has the following advantages over the prior art.

(1) Very stable for a long time.

(2) The effect does not decrease even when hard water containing high concentrations of Ca and Mg is introduced.

(3) Can be used at high temperatures.

(4) Various alkali metal salts can be added.

(5) Stable over a wide range of pH values.

The conventional adjusting solution is difficult to be used in a process in which both the cleaning effect and the adjusting effect are required since the properties decrease when the cleaning agent is added. In the present invention, cleaning agents such as alkali metal salts and ammonium salts can be added without any problem. Other alkali builders and surfactants such as inorganic alkali builders and organic alkali builders can be added to the adjustment liquid of the present invention. In addition, in this invention, a chelating agent and a concentrated phosphate can also be added in order to negate the effect by the cationic component which arises in a concentrated phosphate and a adjustment liquid.

The method of the present invention merely needs to contact the adjusting liquid with the metal surface, and there is no exact limitation on the contact time or temperature of the adjusting liquid. In addition, the adjustment liquid of the present invention can be applied to all kinds of metals such as steel, galvanized steel, aluminum or aluminum alloy and magnesium or magnesium alloy.

Regarding the process of forming the phosphate layer performed after the adjustment according to the present invention, any kind of dipping, spraying, electrolysis, etc. may be applied. As the phosphate layer, any kind of phosphate such as zinc phosphate, manganese phosphate or zinc phosphate can be used without any problem.

Examples and Comparative Examples

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples according to the present invention. In the following examples, the zinc phosphate layer is taken as an example of the phosphate layer, but the present invention can of course also be applied to other kinds of phosphate layers.

[Psalter]

SPC: (cold rolled steel: JIS-G-3141)

EG: (Steel plate coated with zinc on both sides: plating amount 20g / m ² )

GA: (Double coated hot-dip coated with zinc: plating amount 45g / m ² )

Zn-Ni: (Double sided electroplated with nickel-zinc alloy: electroplating volume 20 g / m ² )

Al: (aluminum sheet: JIS-5052)

MP: (magnesium alloy sheet: JIS-H-4201).

[Processing of Specimens]

The alkaline grease removal process was performed by spraying the specimens at 42 ° C. for 120 seconds using FINE CLEANER 1 4460 (trade name Nihon Parkerizing Co., Ltd.) diluted to 2% with tap water.

In the surface adjustment liquid, a different kind of solution was used. The specimen was immersed into the solution.

Phosphate layer was formed using PALBOND L3020 (trade name Nihon Parkerizing Co., Ltd.) diluted to 4.8% with tap water. The specimen was immersed at 42 ° C. for 120 seconds.

After washing with water, deionized water rinsing was carried out by spraying at room temperature for 30 seconds.

[Phosphate layer evaluation]

The phosphate layer was evaluated for the following items. That is, the appearance, weight of layer (C.W.), layer crystal size (C.S.) and P-ratio were measured.

· Appearance: ◎: Excellent and uniform, ○: partially non-uniform, Δ: not uniform, some thin parts, X: many thin parts; XX: No phosphate layer formed.

CW (g / m ² ): weight of phosphate layer ... W1 (g): weight of specimen after formation of phosphate layer, W2 (g): weight of specimen after peeling off phosphate layer.

CW (g / m ² ) = (W1-W2) / (surface area m ² ).

In the case of steel sheets, the phosphate layer was stripped by immersing the specimen in a chromic acid solution, and in the case of galvanized steel sheets by immersing the specimen in a stripping solution containing ammonium-dichromate and ammonia. In the case of aluminum and magnesium sheets, the P content of the zinc phosphate layer was measured by fluorescent X-rays and the C.W. was calculated based on the P content.

 C.S. (μm): Crystal size of the phosphate layer ... The crystal size was determined using a 1500-fold magnified image obtained by scanning electron microscopy (SEM).

P-ratio (%) ... This observation was only performed on SPC steel plates. By observing P (X-ray intensity of phosphoprite) and H (X-ray intensity of hopeite), the P-ratio was determined by the following formula.

P-ratio = P / (P + H).

Table 1 shows the components of the adjustment liquid used in the embodiment of claim 1 of the present invention. Table 2 shows the adjustment liquid used for the comparative example. Commercial products of the monosaccharides, polysaccharides and derivatives thereof used in Tables 1 and 2 were purchased. Examples of the displacement groups include glucose of the following formula (2) as an example of the saccharide of the basic structure.

In the case of glucose, a hydroxyl group can be etherified at positions R ¹ , R ² and R ³ . In the examples, the substituents and degree of substitution (the number of hydroxy groups substituted by substituents per unit of basic saccharide structure) to maintain the effect varied. In addition, sodium salts were used for low water-soluble monosaccharides, polysaccharides and derivatives. After the adjustment solution was kept at room temperature for 10 days, a time durability test (durability test) of the prepared adjustment solution was performed.

Example 1

100 ml of 1 mol / L zinc sulfate solution and 100 ml of 1 mol / L sodium hydrogen phosphate solution were alternately added at 50 ° C. to 1 L of 0.5 mol / L iron (II) sulfate solution to obtain a precipitate. The solution with the precipitate was held at 90 ° C. for 1 hour to complete the settling and then rinsed 10 times by decanting. X-ray diffraction analysis of the precipitate after filtration and drying revealed it to be phosphophyllite (Zn ₂ Fe (PO ₄ ) ₂ .4H ₂ O) partially containing iron phosphate. To 1 kg of phosphophyllite, 50 g of a solution prepared by diluting the monosaccharides, polysaccharides and derivatives given in Table 1 with 10% by weight of isopropyl alcohol and water was added thereto, and then, using 0.5 mm diameter zirconia beads, Grinding in a ball mill for about 1 hour. After milling, the crude liquid to be used in this example was prepared and the density of phosphopyrite in the suspension was adjusted to 1 g / L with tap water. The average particle size suspended in the liquid was 0.5 mm when measured using a laser-diffraction / scattering particle-size-dispersion analyzer (LA-920: manufactured by Horiba Seisakusho).

Example 2

100 ml of 1 mol / L zinc sulfate solution and 100 ml of 1 mol / L sodium hydrogen phosphate solution were alternately added at 50 ° C. to 1 L of 0.5 mol / L iron (II) sulfate solution to obtain a precipitate. The solution with the precipitate was held at 90 ° C. for 1 hour to complete the settling and then rinsed 10 times by decanting. X-ray diffraction analysis of the precipitate after filtration and drying revealed it to be phosphophyllite (Zn ₂ Fe (PO ₄ ) ₂ .4H ₂ O) partially containing iron phosphate. To 1 kg of a solution prepared by diluting the monosaccharides, polysaccharides, and derivatives given in Table 1 with 10% by weight of isopropyl alcohol and water, 100 g of the phosphopyrite was added, and then about 1 using 0.5 mm diameter zirconia beads. Grinded in a ball mill for hours. After milling, the crude liquid to be used in this example was prepared and the density of phosphopyrite in the suspension was adjusted to 1 g / L with tap water. The average particle size suspended in the liquid was 0.5 μm as measured using the laser-diffraction / scattering particle-size-dispersion analyzer.

Example 3

100 ml of 1 mol / L zinc sulfate solution and 100 ml of 1 mol / L sodium hydrogen phosphate solution were alternately added at 50 ° C. to 1 L of 0.5 mol / L iron (II) sulfate solution to obtain a precipitate. The solution with the precipitate was held at 90 ° C. for 1 hour to complete the settling and then rinsed 10 times by decanting. X-ray diffraction analysis of the precipitate after filtration and drying revealed it to be phosphophyllite (Zn ₂ Fe (PO ₄ ) ₂ .4H ₂ O) partially containing iron phosphate. To 1 kg of phosphophyllite, 100 g of a solution prepared by diluting the monosaccharides, polysaccharides and derivatives given in Table 1 to 10% by weight of water was added, followed by ball milling for about 1 hour using 0.5 mm diameter zirconia beads. Pulverized. The average particle size suspended in the liquid was 0.5 μm as measured using the laser-diffraction / scattering particle-size-dispersion analyzer. In addition, 0.5 g / L of sodium nitrite reagent was added as an alkali salt to obtain an adjustment liquid to be used.

Example 4

A precipitate was produced by alternating 100 ml of 1 mol / L zinc sulfate solution and 100 ml of 1 mol / L sodium hydrogen phosphate solution at 50 ° C. to 1 L of 0.5 mol / L iron (II) sulfate solution. The solution with the precipitate was held at 90 ° C. for 1 hour to complete the settling and then rinsed 10 times by decanting. X-ray diffraction analysis of the precipitate after filtration and drying revealed it to be phosphophyllite (Zn ₂ Fe (PO ₄ ) ₂ .4H ₂ O) partially containing iron phosphate. To 1 kg of a solution prepared by diluting the monosaccharides, polysaccharides and derivatives given in Table 1 to 10% by weight of water, 50 g of the phosphophyllite was added, followed by ball milling for about 1 hour using 0.5 mm diameter zirconia beads. Pulverized. After grinding, the adjustment liquid to be used in this example was prepared by adjusting the density of phosphopyrite in the liquid to 1 g / L using tap water. The average particle size suspended in the liquid was 0.5 μm as measured using the laser-diffraction / scattering particle-size-dispersion analyzer. Furthermore, 0.5 g / L of magnesium sulfate heptahydrate was added as an alkali salt, and the adjustment liquid to be used was obtained.

Example 5

A precipitate was produced by alternating 100 ml of 1 mol / L zinc sulfate solution and 100 ml of 1 mol / L sodium hydrogen phosphate solution at 50 ° C. to 1 L of 0.5 mol / L iron (II) sulfate solution. The solution with the precipitate was held at 90 ° C. for 1 hour to complete the settling and then rinsed 10 times by decanting. X-ray diffraction analysis of the precipitate after filtration and drying revealed it to be phosphophyllite (Zn ₂ Fe (PO ₄ ) ₂ .4H ₂ O) partially containing iron phosphate. To 1 kg of a solution prepared by diluting the monosaccharides, polysaccharides and derivatives given in Table 1 to 10% by weight of water, 50 g of the phosphophyllite was added, followed by ball milling for about 1 hour using 0.5 mm diameter zirconia beads. Pulverized. After grinding, the adjustment liquid to be used in this example was prepared by adjusting the density of phosphopyrite in the liquid to 1 g / L using tap water. The average particle size suspended in the liquid was 0.5 μm as measured using the laser-diffraction / scattering particle-size-dispersion analyzer.

Example 6

A precipitate was produced by alternating 100 ml of 1 mol / L zinc sulfate solution and 100 ml of 1 mol / L sodium hydrogen phosphate solution at 50 ° C. to 1 L of 0.5 mol / L iron (II) sulfate solution. The solution with the precipitate was held at 90 ° C. for 1 hour to complete the settling and then rinsed 10 times by decanting. X-ray diffraction analysis of the precipitate after filtration and drying revealed it to be phosphophyllite (Zn ₂ Fe (PO ₄ ) ₂ .4H ₂ O) partially containing iron phosphate. To 1 kg of the solution prepared by diluting the monosaccharides, polysaccharides and derivatives given in Table 1 to 10% by weight with water, 1 kg of the phosphophyllite was added, followed by ball milling for about 1 hour using 0.5 mm diameter zirconia beads. Pulverized. After grinding, the surface-treated treatment liquid to be used in this example was prepared by adjusting the density of phosphophyllite in the liquid to 1 g / L with tap water. The average particle size suspended in the liquid was 0.5 μm as measured using the laser-diffraction / scattering particle-size-dispersion analyzer.

Example 7

1 kg of Zn ₃ Fe (PO ₄ ) ₂ · 4H ₂ O was added to 1 kg of a 10 wt% solution of monosaccharides, polysaccharides and derivatives diluted with water, and then in a ball mill for about 1 hour using 0.5 mm diameter zirconia beads. Pulverized. After grinding, the adjustment liquid to be used in this example was prepared by adjusting the density of Zn ₃ Fe (PO ₄ ) ₂ .4H ₂ O in the liquid to 1 g / L using tap water. The average particle size suspended in the liquid was 0.6 μm as measured using the laser-diffraction / scattering particle-size-dispersion analyzer.

Example 8

To 1 kg of Zn ₃ Fe (PO ₄ ) ₂ 4H ₂ O reagent, add 10 g of 10 wt% aqueous solution of monosaccharides, polysaccharides and derivatives given in Table 1 and ball mill for about 1 hour using 10 mm diameter zirconia beads. Pulverized in. After grinding, the density of Zn ₃ Fe (PO ₄ ) ₂ .4H ₂ O in the liquid was adjusted to 1 g / L using tap water. After the adjustment, the average particle size suspended in the liquid was 1.2 μm as measured using the laser-diffraction / scattering particle-size-dispersion analyzer. Subsequently, 5 g / L of sodium metasilicate reagent was added as alkali to obtain a crude liquid to be used.

Example 9

To 1 L of 0.1 mol / L calcium nitrate solution at 50 ° C., 200 ml of 1 mol / L zinc nitrate solution and 200 ml of 1 mol / L sodium-1-hydrogenphosphate solution were added to produce a precipitate. The solution with the precipitate was held at 90 ° C. for 1 hour to complete the settling and then rinsed 10 times by decanting. X-ray diffraction analysis of the precipitate after filtration and drying revealed it to be sholzite: Zn ₂ Ca (PO ₄ ) ₂ .2H ₂ O. To 1 kg of this schulzite, 10 g of a solution prepared by diluting the monosaccharides, polysaccharides and derivatives given in Table 1 to 10% by weight of water was added, followed by zirconia beads of 0.5 mm diameter for about 1 hour. Grinding in a ball mill. After grinding, the density of schulzite in the liquid was adjusted to 10 g / L using tap water. The average particle size suspended in the liquid was 0.4 μm as measured using the laser-diffraction / scattering particle-size-dispersion analyzer. Sodium carbonate reagent was added at a concentration of 1 g / L to obtain a crude solution to be used.

Example 10

To 1 L of 0.1 mol / L calcium nitrate solution at 50 ° C., 200 ml of 1 mol / L zinc nitrate solution and 200 ml of 1 mol / L sodium-1-hydrogenphosphate solution were added to produce a precipitate. The solution with the precipitate was held at 90 ° C. for 1 hour to complete the settling and then rinsed 10 times by decanting. X-ray diffraction analysis of the precipitate after filtration and drying revealed it to be sholzite: Zn ₂ Ca (PO ₄ ) ₂ .2H ₂ O. To 1 kg of this schulzite, 10 g of a solution prepared by diluting the monosaccharides, polysaccharides and derivatives given in Table 1 to 10% by weight of water was added, followed by zirconia beads of 0.5 mm diameter for about 1 hour. Grinding in a ball mill. After grinding, the density of schulzite in the liquid was adjusted to 5 g / L using tap water. The average particle size suspended in the liquid was 0.4 μm as measured using the laser-diffraction / scattering particle-size-dispersion analyzer. In addition, a tertiary sodium phosphate reagent was added in an amount of 10 g / L as alkali and polyoxyethylene-nonylphenol ether as an surfactant was added in an amount of 2 g / L to obtain an adjustment liquid to be used. In this case, the smeared specimens were used without degreasing and cleaning and adjustment were carried out simultaneously.

Comparative Example 1

Prepalene ZN (trade name of Nihon Parkerizing Co. Ltd.), which has been used in the prior art as an adjustment liquid in an aqueous solution, was used as an adjustment liquid under standard conditions.

Comparative Example 2

To the Prepalene Zn solution, 7-hydrated magnesium sulfate reagent was added at a concentration of 0.5 g / L to obtain a crude solution to be used.

Comparative Example 3

A precipitate was produced by alternating 100 ml of 1 mol / L zinc sulfate solution and 100 ml of 1 mol / L sodium hydrogen phosphate solution at 50 ° C. to 1 L of 0.5 mol / L iron (II) sulfate solution. The solution with the precipitate was held at 90 ° C. for 1 hour to complete the settling and then rinsed 10 times by decanting. X-ray diffraction analysis of the precipitate after filtration and drying revealed it to be phosphophyllite (Zn ₂ Fe (PO ₄ ) ₂ .4H ₂ O) partially containing iron phosphate. This phosphophyllite was used in a ball mill until the average particle size of particles suspended in the liquid using 0.5 mm diameter zirconia beads was less than 0.5 μm as measured using the laser-diffraction / scattering particle-size-dispersion analyzer. Pulverized. After grinding, the adjustment liquid to be used in this comparative example was prepared by adjusting the density of phosphopyrite to 1 g / L using tap water.

[Comparative Example 4]

A precipitate was produced by alternating 100 ml of 1 mol / L zinc sulfate solution and 100 ml of 1 mol / L sodium hydrogen phosphate solution at 50 ° C. to 1 L of 0.5 mol / L iron (II) sulfate solution. The solution with the precipitate was held at 90 ° C. for 1 hour to complete the settling and then rinsed 10 times by decanting. X-ray diffraction analysis of the precipitate after filtration and drying revealed it to be phosphophyllite (Zn ₂ Fe (PO ₄ ) ₂ .4H ₂ O) partially containing iron phosphate. This phosphophyllite was ground in mortar for about 2 minutes. After grinding, it was diluted with tap water, filtered through a 5 μm filter paper and the filtrate was discarded. The precipitate obtained was dried at 80 ° C. for 1 hour and 50 g of a 10 wt% solution obtained by diluting the monosaccharides, polysaccharides and derivatives given in Table 1 with water and isopropyl alcohol was added to 1 kg of this dried powder.

The adjustment liquid was obtained by adjusting the density of the said dried powder to 1 g / L using tap water. The average particle size of the particles suspended in the liquid was 6.5 μm as measured using the laser-diffraction / scattering particle-size-dispersion analyzer.

Table 3 shows the properties of the phosphate layer formed according to the examples, wherein the phosphate layer is the zinc phosphate layer in all examples.

Table 4 shows the characteristics of the phosphate layer formed according to the comparative example, and in all the comparative examples, the phosphate layer is also a zinc phosphate layer.

From Tables 3 and 4, as shown in Table 4, the conventional liquids have drawbacks in terms of time durability, which is remarkably improved when treated with the adjustment liquid according to the present invention as shown in Table 3. From Comparative Example 3 and Examples 1 and 2, the effect of monosaccharides, polysaccharides and derivatives thereof on surface adjustment can be clearly seen. Comparative Example 3 was much lower than Example 1 immediately after preparation of the adjusting liquid, but was superior to the conventional liquid of Comparative Example 1.

However, in Comparative Example 3, it was difficult to pulverize the phosphate of the divalent or trivalent metal, and also after 10 days of liquid preparation, precipitation of the phosphate of the divalent or trivalent metal occurred. This is due to the reaggregation of the phosphates of divalent or trivalent metals, since they do not contain monosaccharides, polysaccharides or derivatives thereof. In addition, it was difficult to obtain dense and fine crystals in the comparative example compared to the corresponding example.

Table 5 shows the components of the adjustment liquid of claim 2 of the present invention. In the present invention, the pH value of the adjusting liquid is not very important. However, if it is too acidic, there is a risk that the phosphate solid particles of divalent and trivalent metals are decomposed into the adjusting liquid. In order to prevent this, it is preferable to neutralize the adjustment liquid by, for example, adding NaOH when it is too acidic. Durability test was carried out after maintaining the adjustment solution for 10 days at room temperature.

Example 11

A precipitate was produced by alternating 100 ml of 1 mol / L zinc sulfate solution and 100 ml of 1 mol / L sodium hydrogen phosphate solution at 50 ° C. to 1 L of 0.5 mol / L iron (II) sulfate solution. The solution with the precipitate was held at 90 ° C. for 1 hour to complete the settling and then rinsed 10 times by decanting. X-ray diffraction analysis of the precipitate after filtration and drying revealed it to be phosphophyllite (Zn ₂ Fe (PO ₄ ) ₂ .4H ₂ O) partially containing iron phosphate. To 1 kg of phosphophyllite, 2 g of the phosphorus compound in Table 5 was added in the form of a 10 wt% diluted aqueous solution and ground in a ball mill for about 1 hour using 0.5 mm diameter zirconia beads. After grinding, the density of phosphopyrite was adjusted to 5 g / L using tap water. The mean particle size of the suspended particles was 0.5 μm as measured using the laser-diffraction / scattering particle-size-dispersion analyzer. In addition, magnesium sulfate 7-hydrate reagent as an alkali was added as 0.5 g / L to obtain a crude liquid to be used.

Example 12

A precipitate was produced by alternating 100 ml of 1 mol / L zinc sulfate solution and 100 ml of 1 mol / L sodium hydrogen phosphate solution at 50 ° C. to 1 L of 0.5 mol / L iron (II) sulfate solution. The solution with the precipitate was held at 90 ° C. for 1 hour to complete the settling and then rinsed 10 times by decanting. X-ray diffraction analysis of the precipitate after filtration and drying revealed it to be phosphophyllite (Zn ₂ Fe (PO ₄ ) ₂ .4H ₂ O) partially containing iron phosphate. To 1 kg of phosphophyllite, 1 kg of the phosphorus compound in Table 5 was added in the form of a 10 wt% diluted aqueous solution and ground in a ball mill for about 1 hour using 0.5 mm diameter zirconia beads. After grinding, the density of phosphopyrite was adjusted to 1 g / L using tap water. The mean particle size of the suspended particles was 0.5 μm as measured using the laser-diffraction / scattering particle-size-dispersion analyzer. In addition, sodium meta-silicate reagent as alkali was added as 1 g / L to obtain a crude liquid to be used.

Example 13

A precipitate was produced by alternating 100 ml of 1 mol / L zinc sulfate solution and 100 ml of 1 mol / L sodium hydrogen phosphate solution at 50 ° C. to 1 L of 0.5 mol / L iron (II) sulfate solution. The solution with the precipitate was held at 90 ° C. for 1 hour to complete the settling and then rinsed 10 times by decanting. X-ray diffraction analysis of the precipitate after filtration and drying revealed it to be phosphophyllite (Zn ₂ Fe (PO ₄ ) ₂ .4H ₂ O) partially containing iron phosphate. To 1 kg of a 10 wt% aqueous solution of the phosphorus compounds given in Table 5, 200 g of the phosphopyrite was added and ground in a ball mill for about 1 hour using 10 mm diameter zirconia beads. After grinding, the adjustment liquid to be used in this example was prepared by adjusting the density of phosphopyrite in the liquid to 1 g / L using tap water. The average particle size of suspended particles in the liquid was 1.7 μm as measured using the laser-diffraction / scattering particle-size-dispersion analyzer.

Example 14

To 1 kg of Zn ₃ Fe (PO ₄ ) ₂ .4H ₂ O reagent, 100 g of a 10 wt% aqueous solution of the phosphorus compounds given in Table 5 were added and ground in a ball mill for about 1 hour using zirconia beads of 0.5 mm in diameter. After grinding, the density of Zn ₃ Fe (PO ₄ ) ₂ .4H ₂ O was adjusted to 5 g / L using tap water. The average particle size suspended in the liquid was 0.6 μm as measured using the laser-diffraction / scattering particle-size-dispersion analyzer. In addition, sodium carbonate reagent was added at a concentration of 5 g / L to prepare an adjustment liquid to be used.

Example 15

At 50 ° C., to 1 L of calcium nitrate 0.1 mol / L solution, 200 mL of 1 mol / L zinc nitrate solution and 200 mL of 1 mol / L sodium hydrogen phosphate were added to produce a precipitate. The solution with the precipitate was held at 90 ° C. for 1 hour to complete the settling and then rinsed 10 times by decanting. X-ray diffraction analysis of the precipitate after filtration and drying revealed it to be schulzite (Zn ₂ Ca (PO ₄ ) ₂ .2H ₂ O). To 1 kg of a 10 wt% aqueous solution of the phosphorus compounds given in Table 5, 1 kg of the schollite was added and ground in a ball mill for about 1 hour using 0.5 mm diameter zirconia beads. After grinding, the density of the schollite was adjusted to 10 g / L using tap water. The average particle size suspended in the liquid was 0.5 μm as measured using the laser-diffraction / scattering particle-size-dispersion analyzer. In addition, a tertiary sodium phosphate reagent was added in an amount of 10 g / L as an alkali and polyoxyethylene-nonylphenol ether as a surfactant in an amount of 2 g / L to obtain an adjustment liquid to be used. In this case, the specimens were used without degreasing to simultaneously perform cleaning and adjustment.

[Comparative Example 5]

A precipitate was produced by alternating 100 ml of 1 mol / L zinc sulfate solution and 100 ml of 1 mol / L sodium hydrogen phosphate solution at 50 ° C. to 1 L of 0.5 mol / L iron (II) sulfate solution. The solution with the precipitate was held at 90 ° C. for 1 hour to complete the settling and then rinsed 10 times by decanting. X-ray diffraction analysis of the precipitate after filtration and drying revealed it to be phosphophyllite (Zn ₂ Fe (PO ₄ ) ₂ .4H ₂ O) partially containing iron phosphate. This phosphophyllite was ground in mortar for about 2 minutes. After grinding, the mixture was diluted with tap water, filtered through a 5 μm filter paper, and the filtrate was discarded. The precipitate obtained was dried at 80 ° C. for 1 hour to obtain a powdery product. 100 g of this powder was then added to 500 g of a 10% by weight aqueous solution of the phosphorus compounds given in Table 2, and a crude liquid was prepared by adjusting the density of the powder to 1 g / L using tap water. The average particle size suspended in the liquid was 6.5 μm as measured using the laser-diffraction / scattering particle-size-dispersion analyzer.

Table 6 shows the characteristic of the phosphate layer formed when the adjustment liquid of Examples 11-15 was used. Properties of the phosphate layer formed according to Comparative Example 5 are shown in Table 4.

From Table 6 and Table 4, it can be seen that the adjustment liquid of the present invention is significantly improved in terms of time durability, which was a disadvantage of the adjustment liquid according to the prior art. From the results of Comparative Example 3 and Example 13, the effect of the phosphorus compound can be clearly seen.

Immediately after being prepared as the adjusting liquid, Comparative Example 3 had lower characteristics than Example 11, but the surface adjusting effect was better or boiling than that of Comparative Example 1. In Comparative Example 3, however, it was very difficult to pulverize the phosphate of the divalent or trivalent metal and after 10 days of liquid preparation, the phosphate of the divalent or trivalent metal precipitated. This is due to the reaggregation of phosphates of divalent or trivalent metals, since it does not contain orthophosphoric acid, polyphosphoric acid or organophosphonic acid compounds.

Table 7 shows the components of the adjustment liquid of claim 3 of the present invention. In Tables 7 and 2, the aqueous high molecular compounds of polymers of vinyl acetate or derivatives thereof, copolymers of vinyl acetate and polymerizable monomers and vinyl acetate are expressed only as aqueous high molecular compounds. The polymers and their derivatives were polymerized with vinyl acetate using peroxides as initiators and functional groups were added by soap or acetal chemistry. In addition, copolymers of vinyl acetate and polymerizable monomers were synthesized by polymerizing vinyl acetate with individual monomers.

The time durability test was performed after maintaining the adjustment solution at room temperature for 10 days.

Example 16

A precipitate was produced by alternating 100 ml of 1 mol / L zinc sulfate solution and 100 ml of 1 mol / L sodium hydrogen phosphate solution at 50 ° C. to 1 L of 0.5 mol / L iron (II) sulfate solution. The solution with the precipitate was held at 90 ° C. for 1 hour to complete the settling and then rinsed 10 times by decanting. X-ray diffraction analysis of the precipitate after filtration and drying revealed it to be phosphophyllite (Zn ₂ Fe (PO ₄ ) ₂ .4H ₂ O) partially containing iron phosphate. To 1 kg of phosphophyllite, 2 g of a 10% by weight solution of the aqueous polymeric compound given in Table 7 diluted with water was added and ground in a ball mill for about 1 hour using 0.5 mm diameter zirconia beads. After grinding, the density of phosphopyrite was adjusted to 5 g / L using tap water. The mean particle size of the suspended particles was 0.5 μm as measured using the laser-diffraction / scattering particle-size-dispersion analyzer. In addition, sodium meta-silicate reagent as alkali was added as 0.5 g / L to obtain a crude liquid to be used.

Example 17

A precipitate was produced by alternating 100 ml of 1 mol / L zinc sulfate solution and 100 ml of 1 mol / L sodium hydrogen phosphate solution at 50 ° C. to 1 L of 0.5 mol / L iron (II) sulfate solution. The solution with the precipitate was held at 90 ° C. for 1 hour to complete the settling and then rinsed 10 times by decanting. X-ray diffraction analysis of the precipitate after filtration and drying revealed it to be phosphophyllite (Zn ₂ Fe (PO ₄ ) ₂ .4H ₂ O) partially containing iron phosphate. 100 g of this phosphophyllite was added to 500 g of a 10 wt% aqueous solution of the aqueous polymer compound given in Table 7 and ground in a ball mill for about 1 hour using 0.5 mm diameter zirconia beads. After pulverization, the density of phosphopyrite was adjusted to 1 g / L with tap water to obtain an adjustment liquid to be used. The mean particle size of the suspended particles in the solution was 0.5 μm as measured using the laser-diffraction / scattering particle-size-dispersion analyzer.

Example 18

To 1 kg of an aqueous 10 wt% aqueous polymer compound given in Table 7, 50 g of Zn ₃ (PO ₄ ) ₂ .4H ₂ O reagent was added and ground in a ball mill for about 1 hour using 0.5 mm diameter zirconia beads. After grinding, the density of Zn ₃ (PO ₄ ) ₂ .4H ₂ O was adjusted to 1 g / L with tap water. The mean particle size of the suspended particles in the solution was 0.5 μm as measured using the laser-diffraction / scattering particle-size-dispersion analyzer. In addition, magnesium sulfate heptahydrate reagent was added as 0.5 g / L to obtain a crude solution to be used.

Example 19

At 50 ° C., to 1 L of calcium nitrate 0.1 mol / L solution, 200 mL of 1 mol / L zinc nitrate solution and 200 mL of 1 mol / L sodium hydrogen phosphate were added to produce a precipitate. The solution with the precipitate was held at 90 ° C. for 1 hour to complete the settling and then rinsed 10 times by decanting. X-ray diffraction analysis of the precipitate after filtration and drying revealed it to be schulzite (Zn ₂ Ca (PO ₄ ) ₂ .2H ₂ O). To 1 kg of a 10 wt% aqueous solution of the aqueous polymeric compound given in Table 7, 500 g of the schizite was added and ground in a ball mill for about 1 hour using 10 mm diameter zirconia beads. After grinding, the density of the schollite was adjusted to 5 g / L with tap water. The average particle size suspended in the liquid was 1.6 μm as measured using the laser-diffraction / scattering particle-size-dispersion analyzer. In addition, sodium carbonate reagent was added as an alkali at a concentration of 5 g / L to obtain a crude liquid to be used.

Example 20

At 50 ° C., to 1 L of calcium nitrate 0.1 mol / L solution, 200 mL of 1 mol / L zinc nitrate solution and 200 mL of 1 mol / L sodium hydrogen phosphate were added to produce a precipitate. The solution with the precipitate was held at 90 ° C. for 1 hour to complete the settling and then rinsed 10 times by decanting. X-ray diffraction analysis of the precipitate after filtration and drying revealed it to be schulzite (Zn ₂ Ca (PO ₄ ) ₂ .2H ₂ O). To 1 kg of this schottzite, 10 g of a 10% by weight aqueous solution of the polymer compound of Table 7 was added and ground in a ball mill for about 1 hour using 0.5 mm diameter zirconia beads. The density of the schollite was adjusted to 30 g / L using tap water. After the adjustment, the average particle size of the particles suspended in the liquid was 0.3 μm as measured using the laser-diffraction / scattering particle-size-dispersion analyzer. In addition, a tertiary sodium phosphate reagent was added in an amount of 10 g / L as an alkali and polyoxyethylene-nonylphenol ether as a surfactant in an amount of 2 g / L to obtain an adjustment liquid to be used. In this case, the specimens were used without degreasing to simultaneously perform cleaning and adjustment.

Comparative Example 6

A precipitate was produced by alternating 100 ml of 1 mol / L zinc sulfate solution and 100 ml of 1 mol / L sodium hydrogen phosphate solution at 50 ° C. to 1 L of 0.5 mol / L iron (II) sulfate solution. The solution with the precipitate was held at 90 ° C. for 1 hour to complete the settling and then rinsed 10 times by decanting. X-ray diffraction analysis of the precipitate after filtration and drying revealed it to be phosphophyllite (Zn ₂ Fe (PO ₄ ) ₂ .4H ₂ O) partially containing iron phosphate. This phosphophyllite was ground in mortar for about 2 minutes. After grinding, the mixture was diluted with tap water, filtered through a 5 μm filter paper, and the filtrate was discarded. The precipitate obtained was dried at 80 ° C. for 1 hour to obtain a powdery product. 100 g of this powder was then added to 500 g of an aqueous 10% by weight aqueous solution of the aqueous high molecular compound given in Table 2, and an adjustment liquid to be used was prepared by adjusting the density of the powder to 1 g / L using tap water. The average particle size suspended in the liquid was 6.5 μm as measured using the laser-diffraction / scattering particle-size-dispersion analyzer.

Table 8 shows the characteristic of the phosphate layer formed using the adjustment liquid of Table 7. Table 4 shows the characteristic of the phosphate layer obtained using the adjustment liquid of the comparative example 6.

Table 8 and Table 4 confirm that the adjustment treatment liquid of the present invention significantly improved the durability. From Comparative Example 3 and Example 17, the high performance of the aqueous high molecular compound is clearly seen. In addition, Comparative Example 3 was lower in properties than Example 16, but was superior to the conventional adjustment liquid as shown in Comparative Example 1.

In Comparative Example 3, however, it was very difficult to pulverize the phosphate of the divalent or trivalent metal and after 10 days of liquid preparation, the phosphate of the divalent or trivalent metal precipitated. This sedimentation is due to the aggregation of phosphate powders of divalent or trivalent metals, which occurs because Comparative Example 3 does not contain an aqueous high molecular compound.

Table 9 shows the components of the adjustment liquid of claim 4 of the present invention. Promoting components in Table 9 and Comparative Example 7 were prepared using ammonium bisulfate as catalyst. There is no restriction | limiting in pH in this invention, but when pH of a polymer or a copolymer is too low, it is preferable to neutralize with sodium hydroxide beforehand in order to prevent decomposition | disassembly of a phosphate powder into a liquid. The time durability test was performed after the adjustment liquid was held at room temperature for 10 days.

Example 21

A precipitate was produced by alternating 100 ml of 1 mol / L zinc sulfate solution and 100 ml of 1 mol / L sodium hydrogen phosphate solution at 50 ° C. to 1 L of 0.5 mol / L iron (II) sulfate solution. The solution with the precipitate was held at 90 ° C. for 1 hour to complete the settling and then rinsed 10 times by decanting. X-ray diffraction analysis of the precipitate after filtration and drying revealed it to be phosphophyllite (Zn ₂ Fe (PO ₄ ) ₂ .4H ₂ O) partially containing iron phosphate. To 1 kg of phosphophyllite, 1 g of a 10% by weight aqueous solution previously diluted with the polymers or copolymers given in Table 9 was added and ground in a ball mill for about 1 hour using 0.5 mm diameter zirconia beads. After grinding, the density of suspended phosphophyllite was adjusted to 10 g / L with tap water. The average particle size of the particles suspended in the liquid was 0.5 μm as measured using the laser-diffraction / scattering particle-size-dispersion analyzer. In addition, sodium nitrite reagent was added as alkali as 0.5 g / L to obtain an adjustment liquid to be used.

Example 22

A precipitate was produced by alternating 100 ml of 1 mol / L zinc sulfate solution and 100 ml of 1 mol / L sodium hydrogen phosphate solution at 50 ° C. to 1 L of 0.5 mol / L iron (II) sulfate solution. The solution with the precipitate was held at 90 ° C. for 1 hour to complete the settling and then rinsed 10 times by decanting. X-ray diffraction analysis of the precipitate after filtration and drying revealed it to be phosphophyllite (Zn ₂ Fe (PO ₄ ) ₂ .4H ₂ O) partially containing iron phosphate. 100 g of the phosphopyrite was added to 500 g of the 10 wt% aqueous solution of the polymer or copolymer of Table 9, and ground in a ball mill using 0.5 mm diameter zirconia beads for about 1 hour. After grinding, the density of phosphopyrite was adjusted to 1 g / L with tap water to obtain an adjustment liquid to be used. The average particle size of the particles suspended in the liquid was 0.5 μm as measured using the laser-diffraction / scattering particle-size-dispersion analyzer.

Example 23

A precipitate was produced by alternating 100 ml of 1 mol / L zinc sulfate solution and 100 ml of 1 mol / L sodium hydrogen phosphate solution at 50 ° C. to 1 L of 0.5 mol / L iron (II) sulfate solution. The solution with the precipitate was held at 90 ° C. for 1 hour to complete the settling and then rinsed 10 times by decanting. X-ray diffraction analysis of the precipitate after filtration and drying revealed it to be phosphophyllite (Zn ₂ Fe (PO ₄ ) ₂ .4H ₂ O) partially containing iron phosphate. 25 g of the phosphopyrite was added to 1 kg of an aqueous 10 wt% polymer or copolymer of Table 9 and ground in a ball mill for about 1 hour using 0.5 mm diameter zirconia beads. After grinding, the density of phosphophyllite was adjusted to 0.5 g / L using tap water. The average particle size of the particles suspended in the liquid was 0.5 μm as measured using the laser-diffraction / scattering particle-size-dispersion analyzer. In addition, magnesium sulfate heptahydrate reagent was added at a concentration of 0.5 g / L to obtain a crude solution to be used.

Example 24

At 50 ° C., to 1 L of calcium nitrate 0.1 mol / L solution, 200 mL of 1 mol / L zinc nitrate solution and 200 mL of 1 mol / L sodium hydrogen phosphate were added to produce a precipitate. The solution with the precipitate was held at 90 ° C. for 1 hour to complete the settling and then rinsed 10 times by decanting. X-ray diffraction analysis of the precipitate after filtration and drying revealed it to be schulzite (Zn ₂ Ca (PO ₄ ) ₂ .2H ₂ O). To 1 kg of this schottzite, 1.5 g of a 10% by weight aqueous solution of the polymer or copolymer of Table 9 was added and ground in a ball mill for about 1 hour using 0.5 mm diameter zirconia beads. After grinding, the density of the schollite was adjusted to 10 g / L using tap water. The average particle size of the suspended particles in the solution was 0.6 μm as measured using the laser-diffraction / scattering particle-size-dispersion analyzer. In addition, 0.5 g / L of sodium carbonate reagent was added as alkali to obtain the adjustment liquid to be used.

Example 25

At 50 ° C., to 1 L of calcium nitrate 0.1 mol / L solution, 200 mL of 1 mol / L zinc nitrate solution and 200 mL of 1 mol / L sodium hydrogen phosphate were added to produce a precipitate. The solution with the precipitate was held at 90 ° C. for 1 hour to complete the settling and then rinsed 10 times by decanting. X-ray diffraction analysis of the precipitate after filtration and drying revealed it to be schulzite (Zn ₂ Ca (PO ₄ ) ₂ .2H ₂ O). To 1 kg of this schulzite, 20 g of a 10% by weight aqueous solution of the polymer or copolymer of Table 9 was added and ground in a ball mill for about 1 hour using 0.5 mm diameter zirconia beads. After grinding, the density of schulzite was adjusted to 5 g / L using tap water. The average particle size of the suspended particles in the solution was 0.6 μm as measured using the laser-diffraction / scattering particle-size-dispersion analyzer. In addition, 10 g / L of the tertiary sodium phosphate reagent was added as alkali to obtain the adjustment liquid to be used.

Example 26

1 kg of Zn ₃ (PO ₄ ) ₂ .4H ₂ O reagent was added to 1 kg of an aqueous 10 wt% polymer or copolymer of Table 9 and ground in a ball mill for about 1 hour using zirconia beads of 10 mm in diameter. After grinding, the density of the Zn ₃ (PO ₄ ) ₂ .4H ₂ O suspended particles was adjusted to 1 g / L using tap water. The average particle size suspended in the prepared solution was 1.2 μm as measured using the laser-diffraction / scattering particle-size-dispersion analyzer. In addition, a sodium metasilicate reagent was added at a concentration of 5 g / L as an alkali, and polyoxyethylene-nonylphenol ether was added at a concentration of 2 g / L as a surfactant to obtain an adjustment liquid to be used. In this case, the specimens were used without degreasing in order to simultaneously perform cleaning and adjustment.

Example 27

To 1 kg of Zn ₃ (PO ₄ ) ₂ .4H ₂ O reagent, 50 g of a 10 wt% aqueous solution of the polymers or copolymers of Table 9 were added and ground in a ball mill for about 1 hour using zirconia beads of 0.5 mm in diameter. The density of the suspended particles of Zn ₃ (PO ₄ ) ₂ .4H ₂ O was adjusted to 1 g / L using tap water to obtain an adjustment liquid to be used. The average particle size suspended in the liquid was 0.5 μm as measured using the laser-diffraction / scattering particle-size-dispersion analyzer.

Comparative Example 7

A precipitate was produced by alternating 100 ml of 1 mol / L zinc sulfate solution and 100 ml of 1 mol / L sodium hydrogen phosphate solution at 50 ° C. to 1 L of 0.5 mol / L iron (II) sulfate solution. The solution with the precipitate was held at 90 ° C. for 1 hour to complete the settling and then rinsed 10 times by decanting. X-ray diffraction analysis of the precipitate after filtration and drying revealed it to be phosphophyllite (Zn ₂ Fe (PO ₄ ) ₂ .4H ₂ O) partially containing iron phosphate. This phosphophyllite was ground in mortar for about 2 minutes. After grinding, it was diluted with tap water, filtered through a 5 μm filter paper and the filtrate was discarded. The precipitate obtained was dried at 80 ° C. for 1 hour to obtain a powder. To 1 kg of this precipitated powder, 100 g of a 10 wt% aqueous solution of the polymer or copolymer of Table 2 was added. The adjustment liquid was obtained by adjusting the density of this phosphophyllite particle to 1 g / L using tap water. The average particle size of the particles suspended in the liquid was 6.5 μm as measured using the laser-diffraction / scattering particle-size-dispersion analyzer.

Table 10 shows the characteristic of the phosphate layer formed using the adjustment liquid of an Example. Table 4 shows the characteristic of the phosphate layer formed using the adjustment liquid of the comparative example 7.

From Table 10 and Table 4, it can be seen that the adjustment liquid of the present invention is significantly improved in durability compared to the adjustment liquid of the prior art. Comparing Comparative Example 3 with Examples 22 and 27, the effect of the polymer or copolymer is more pronounced.

Although Comparative Example 3 was lower in characteristics than Example 21, the surface adjustment effect was comparable or better than that of Comparative Example 1. However, in the case of Comparative Example 3, it was difficult to grind the phosphate of the divalent or trivalent metal, and after 10 days of preparation, precipitation of the phosphate of the divalent or trivalent metal occurred. This is due to the reaggregation of the phosphates of divalent or trivalent metals, since they do not contain polymers or copolymers.

As described above, the adjusting liquid of the present invention succeeded in improving the durability of the adjusting liquid of titanium colloid and making the crystal of the phosphate layer more fine than the adjusting liquid according to the prior art. Therefore, the present invention can produce a phosphate layer that is more economically superior to the prior art and better in quality than the prior art.

Claims (10)

A phosphate particle of a metal selected from divalent and trivalent metals, containing at least one phosphate particle having a diameter of less than 5 μm and at least one promoting component selected from monosaccharides, polysaccharides and derivatives thereof, Characterized by not containing a titanium component, Adjusting liquid used for pretreatment before forming a phosphate layer on the metal surface. A phosphate particle of a metal selected from divalent and trivalent metals, containing at least one phosphate particle having a diameter of less than 5 μm and at least one promoting component selected from orthophosphates, polyphosphates and organophosphonic acid compounds, Characterized by not containing a titanium component, Adjusting liquid used for pretreatment before forming a phosphate layer on the metal surface. Phosphate particles of a metal selected from divalent and trivalent metals, selected from one or more of phosphate particles having a diameter of less than 5 μm, and polymers of vinyl acetate, derivatives thereof and copolymers of vinyl acetate with other monomers as accelerating components; Contains one or more water-soluble high molecular compounds, Characterized by not containing a titanium component, Adjusting liquid used for pretreatment before forming a phosphate layer on the metal surface. A phosphate particle of a metal selected from divalent and trivalent metals, wherein at least one phosphate particle having a diameter of less than 5 μm and a copolymer or polymer obtained by polymerizing the following monomer i) with less than 50% by weight of monomer ii) Contains one or more facilitation ingredients selected, Characterized by not containing a titanium component, Modulating liquid used for pretreatment before forming a phosphate layer on the metal surface: Monomer i) A monomer selected from monomers having the following formula (1) or α-, β-unsaturated carboxylic acid monomers. Formula 1

(Wherein R ¹ : H or CH ₃ , R ² : H or C _1-5 alkyl group or C _1-5 hydroxyalkyl group) Monomer ii) Monomer copolymerizable with monomer i). The total concentration of phosphate particles is from 0.001 to 30 g / L, and the divalent and trivalent metals are selected from Zn, Fe, Mn, Ni, Co, Ca and Al. Adjusting liquid used for pretreatment before forming a phosphate layer on the metal surface, characterized by being at least one metal. The adjusting liquid according to any one of claims 1 to 4, wherein the total concentration of the accelerating component is 1 to 2000 ppm, and is used for pretreatment before forming the phosphate layer on the metal surface. The adjustment liquid according to any one of claims 1 to 4, which further contains an alkali metal salt, an ammonium salt or a mixture thereof, and is used for pretreatment before forming a phosphate layer on the metal surface. 8. The compound according to claim 7, wherein the alkali metal salt or ammonium salt is at least one compound selected from orthophosphates, metaphosphates, orthosilicates, metasilicates, carbonates, bicarbonates, nitrates, nitrites, sulfates, borates and salts of organic acids The adjusting liquid used for pretreatment before forming a phosphate layer on the metal surface characterized by the density | concentration of 0.5-20 g / L. A method of adjusting a metal surface before forming a phosphate layer, wherein the metal surface is contacted with the adjusting liquid according to any one of claims 1 to 4 before forming the phosphate layer. 10. The adjustment liquid according to claim 9, wherein the adjustment liquid further contains an alkali builder with at least one additive selected from nonionic surfactants and anionic surfactants in order to impart the cleaning effect of the metal surface as a side effect to the adjustment liquid. Metal surface adjustment method before forming a phosphate layer.