JP2002249883A - Phosphate treatment solution, and method for depositing phosphate film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a treatment solution which enables the deposition of a phosphate film having excellent adhesive properties with paints or elastomers formed on the surface of a metallic material. SOLUTION: The treatment solution contains zinc cations and phosphoric anions, and contains at least one adhesion strengthening agent selected from the following: (i) a film depositing organic matter; (ii) a polymer of vinylphenol in which an aminomethyl group is substituted for an aromatic ring; and (iii) inorganic oxide of elements selected from silicon, aluminum, titanium, and zirconium. This method is performed by a drying method as it is. Namely, a layer of the treatment solution is formed on the surface of a metallic material. After that, the layer of the treatment solution is dried as it is without water- washing. Thus, all nonvolatile matters in the treatment solution layer are chemically reacted with the metallic surface, and remain at the place as they are.

Description

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to a process known under the name of phosphating or phosphating. That is, the present invention relates to a method of coating the surface of a metal material with an adhesive coating containing a phosphate anion and a metal cation. The metal cations at this time include at least those corresponding to the metal material. When the phosphating agent further contains divalent cations forming a water-soluble phosphate, the phosphate film contains these divalent cations.

[0002] A phosphate film is formed by a chemical reaction between the surface of a metal material and an aqueous solution of a phosphating agent. Phosphate films can also be formed with or with the aid of a current flow.

[0003] The phosphating agent and the surface of the metal material are kept at 70 ° C.
If the metal material surface is dried by washing away the phosphating agent remaining on the phosphate film on the surface of the metal material after contacting for 5 seconds or longer, the phosphate film is usually fine crystalline It is. This is particularly noticeable when the metal material surface or the phosphating agent contains a sufficient amount of iron or zinc. On the other hand, when the phosphating agent is applied to the surface of the metal material and then dried without being washed away, a film mainly composed of amorphous is formed.

[0004] The phosphate film formed on the surface of the metal material exhibits the following action (1) or (2). That is, (1) the corrosion resistance of the metal material surface on which the phosphate film is formed is improved as compared with the case where the phosphate film is not formed. This improvement in corrosion resistance is observed as it is or when a protective coating such as paint is formed in a later step. (2) The phosphate coating is an excellent carrier for a cold forming lubricant applied to the outer surface of the metal material.

The main object of the present invention is to provide a phosphate film that does not wash away the phosphating agent to have a further effect in the field of improving corrosion resistance. That is, the present invention is characterized in that the adhesiveness to a coating such as a paint, an elastic polymer, a sealant, etc., which is applied in a subsequent step is improved. In particular, paint, elastic polymer (elastomer),
Excellent when a metal material is plastically deformed after applying a sealant or the like. Here, the sealant refers to a resilient material used for the following applications. That is, (i) when forming a joint with a load, (ii) when not in contact with a chemical substance containing liquid or gas, (iii) when reducing noise and vibration, and (iv) as an insulating material. Time, (v) when filling gaps.

[0006] Hereinafter, in this specification, numerical limits indicate preferred ranges. All percentages, parts, and numerical ratios are based on weight. The term polymer includes oligomers, copolymers, terpolymers. When an object is described in a group or a class, a mixture of two or more in the group or the class is also included. The chemical name of the substance described as a component includes the chemical name at the time of addition. The description of ions in the specification indicates the presence of implicitly contained counter ions for making the whole electrically neutral.

[0007] The term paint in this specification includes enamel, varnish, lacquer, shellac coat, electrostatic material, top coat, clear coat, color coat, auto-deposit coat, radiation cure coat, and sink coat. Is included. Also, the wording of solution, dissolution, and homogeneity, besides the situation in the equilibrium state,
100 hours at a temperature of 18-25 ° C, preferably 1000
Includes situations where phase separation is not visible even after time settling.

The present inventors have accomplished the present invention by adding an adhesion enhancer to an ordinary phosphating solution. That is, the present invention uses a phosphating solution containing one or more adhesion enhancers. Then, a phosphate film is formed on the surface of the metal material by forming a layer of an aqueous solution containing a normal phosphating solution and an adhesion enhancer on the surface of the metal material. Then, the aqueous solution on the surface of the metal material is dried while the aqueous solution layer is still formed on the surface of the metal material without washing away the aqueous solution layer with water. No external electrolysis current is used. A phosphate film containing an adhesion enhancer is formed on the surface of the metal material treated by this method.

[0009] Usual phosphating solutions capable of producing the phosphating solution of the present invention by mixing one or more organic film-forming agents are described in the following US Patent Documents.
That is, U.S. Patent Application No. 08 / 760.023, 08 / 344,829, 08/62
4,623,08 / 464,609,08 / 569,177,08 / 638,268,60 / 036,
606, 08 / 849,704, 08 / 761,173 and PCT / US96 / 19144, PCT
/ US96 / 02677 and the following US patents: US
5,645,650,5,683,816,5,595,611,5,498,300,5,472,
522, 5,451,271, 5,378,292, 5,261,973, 5,143,562,
5,125,989, 5,082,511, 5,073,196, 5,045,130, 5,000,
799, 4,992,116, 4,961,794, 4,927,472, 4,880,467,
4,874,480, 4,849,031, 4,722,753, 4,717,431, 4,673,
444, 4643,778, 4,639,295, 4,637,838, 4,612,060, 4,
596,607, 4,595,424, 4,565,585, 4.559,087, 4,539,05
1, 4,529,451, 4,517,029, 4,515,643, 4,486,241, 4,4
43,273, 4,419,199, 4,419,147, 4,416,705, 4,402,76
5, 4,385,096, 4,377,487, 4,338,141, 4,311,535, 4,2
92,096, 4,289,546, 4,265,677,4,220,486, 4,142,917,
4,108,690, 4,063,968, 3,939,014, 3,932,287, 3,87
0,573, 3,860,455, 3,850,700, 3,839,099, 3,795,548,
3,758,349, 3,723,334,3,723,192, 3,706,604, 3,697,
332, 3,671,332,, 3645,797, 3,619,300, 3,615,912,
3,607,453, 3,573,997, 3,565,699, 3,547,711, 3,533,
859, 3,525,651, 3,519,495, 3,519,494, 3,516,875,
3,515,600, 3,493,400, 3,484,304, Re27,896, 3,467,5
89, 3,454,483, 3,450,579, 3,450,578, 3,450,577, 3,
449,222, 3,444,007, 3,401,065, 3,397,093, 3,397,09
2, 3,380,859, 3,338,755, 3,297,493, 3,294,593, 3,2
68,367, 3,240,633, 3,218,200, 3,197,344, 3,161,54
9, 3,154,438, 3,146,133, 3,133,005, 3,101,286, 3,0
46,165, 3,015,594,3,007,817,2,979,430, 2,891,884,
2,882,189, 2,875,111, 2,840,498, 2,835,618, 2,835,
617, 2,832,707, 2,819,193, 2,813,814, 2,813,813,
2,813,812, 2,798,829, 2,758,949, 2,744,555, 2,743,
204, 2,724,668, 2,702,768, 2,665,231, 2,657,156,
2,609,308, 2,591,479, 2,564,864, 2,540,314, 2,298,
312, 2,298,280, 2,245,609, 2,132,883, 2,121,574,
2,121,520, 2,120,21, 2,114,151, 2,076,869, 1,660,6
61, 1,654,716, 1,651,694, 1,639,694, 1,610,362, 1,
485,025, 1,388,325, 1,377,174, 1,341,100, 1,320,73
4, 1,317,351, 1,292,352, 1,290,476,1,287,605, 1,25
4,264, 1,254,263, 1,248,053, 1,219,526, 1,215,463,
and 1,206,075.

The treatment liquid of the present invention is used in a method of drying as it is (a method of not washing before drying). Therefore, the concentrations of the various components themselves have no significant effect on the corrosion resistance performance. Rather, the total amount of the contained components per unit area of the metal material surface, the ratio of the contained components, and the drying temperature and time are more important. Therefore, in this specification, the components contained in the processing liquid are mainly indicated by the ratio of the components. However, the concentrations of the preferred components are convenient for the preparation of the processing solution, so the concentrations are shown for one component contained.

The treatment liquid of the present invention always contains a phosphate anion. This phosphate anion can be supplied as a + 5-valent phosphorus oxyacid or a water-soluble salt. That TadashiRinsan, metaphosphoric acid and _{H (n + 2) P n} O (3n + 1) ( where n
Is a positive integer of 2 or more).

As is well known, these components are present in equilibrium with each other, and have a strong tendency to equilibrate to orthophosphoric acid or a salt thereof at low temperatures and low concentrations, and to condense phosphate at high temperatures and high concentrations. Or metaphosphate. Primarily for economic reasons, the phosphate ions in the processing solution of the present invention are H ₃ P
Those using orthophosphoric acid represented by O ₄ or a salt thereof are preferred. The concentration of phosphate ions in the processing solution of the present invention is 1.0, 2.0, 4, 6, 8, 11, 15, 20, 25, 30, 3 in 1 L of the processing solution.
3, 36, 39, 41, 44, 50, 53, 56, 58 grams of orthophosphoric acid (hereinafter, the gram concentration in 1 L of processing solution is abbreviated as g / L) is preferred, and the latter order is more preferred. .

When an elastic polymer agent (elastomer) is adhered, the concentration of phosphate ions in the phosphating solution of the present invention is 70, 80, 90, 100, 1
10, 120, 130, 140, 145, 150, 155, 160 g / L or more is desirable, and the later order is more preferred. However, from an economic point of view, the concentration of phosphate ions when depositing the elastomer is 400, 200, 190, 1 in terms of the chemical equivalent of orthophosphoric acid.
85, 180, 175, 170, 165, g / L or less are preferable, and the later order is more preferable. However, for applications other than elastomer deposition, this concentration may be 140, 130, 120, 110,
It is preferably 105, 100, 95, 90, 85, 80, 75, 70, 65, 60, g / L or less, and more preferably the latter order. When determining the phosphate ion concentration, all dissolved pentavalent phosphorus should be converted to the equivalent of orthophosphoric acid without considering the degree of dissociation of phosphoric acid, the formation of complex ions, and the formation of condensed phosphoric acid. You can decide.

The treating agent of the present invention further contains a zinc cation. This can be achieved by adding appropriate zinc to the treating agent or by adding metal zinc, zinc oxide, zinc hydroxide and an acid together. If the surface of the metal material is predominantly zinc, a suitable suitable amount of zinc can be dissolved from the metal material into the treatment solution. However, it is preferable to add a predetermined amount of zinc cation before using it in the metal material in order to reduce the variation in the performance of the film.
Zinc oxide and zinc phosphate are preferred as a zinc source to be added for convenience and for preventing contamination of impurities that fluctuate the performance of the formed film, and economically. It is understood that all zinc added to the treatment liquid is a zinc cation irrespective of the degree of dissociation of ions, formation of complex ions, and the like.

The concentration g of zinc cation in the processing solution of the present invention g
/ L is 0.003: 1.00, 0.005: 1.00, 0.1 as a ratio to the concentration of phosphate ion expressed in equivalent g / L of orthophosphoric acid.
It is preferably at least 007: 1.00, 0.010: 1.00, 0.013: 1.00, and more preferably the order of later. When the application creates a paint coating, the above concentration ratio is 0.015:
1.00, 0.020: 1.00, 0.025: 1.00, 0.029: 1.00, 0.033: 1.
00 or more is preferable, and those in the order of later are more preferable. However, in any of the above cases, the concentration ratio of the processing solution of the present invention is 0.10: 1.00, 0.08: 1.00, 0.06: 1.00, 0.055: 1.0.
It is preferably less than 0, 0.050: 1.00, 0.045: 1.00, 0.040: 1.00, 0.035: 1.00, and more preferably the order is later.

The treatment liquid of the present invention preferably contains a manganese cation. The most preferred manganese cation source is primary manganese oxide. It dissolves in an acidic aqueous solution to form manganese cations. Manganese cation concentration g
/ L to the concentration of phosphate ions expressed in g / L of the equivalent of orthophosphoric acid, 0.01: 1.00, 0.030: 1.00,0.
040: 1.00, 0.045: 1.00, 0.050: 1.00, 0.055: 1.00, 0.06
It is preferably 0: 1.00, 0.065: 1.00, 0.070: 1.00, 0.075: 1.00 or more, and more preferably the order of later.

For use in making paint coatings, this concentration ratio is 0.080: 1.00, 0.085: 1.00, 0.090: 1.
00, 0.095: 1.00 or more is preferable, and the case of the latter order is more preferable. However, from an economic point of view, 0.7: 1.00, 0.5: 1.00, 0.3: 1.00, 0.20: 1.00, 0.1
8: 1.00, 0.16: 1.00, 0.014: 1.00, 0.012: 1.00, 0.10: 1.
It is preferably less than 00, and more preferably the latter order.

The treatment liquid of the present invention preferably contains a nickel cation. The source is preferably nickel phosphate. The ratio of the concentration of nickel cation, g / L, to the concentration of phosphate ion, expressed as g / L of the equivalent of orthophosphoric acid, is 0.
003: 1.00, 0.005: 1.00, 0.007: 1.00, 0.010: 1.00, 0.01
The ratio is preferably 5: 1.00, 0.020: 1.00, 0.025: 1.00 or more, and more preferably the order of later.

For use in making paint coatings, this ratio is more preferably at least 0.029: 1.00, more preferably at least 0.03: 1.00.
2: 1.00 is even more preferred. However, from an economic point of view, this nickel: phosphoric acid ratio is
0.10: 1.00, 0.080: 1.00, 0.075: 1.00, 0.070: 1.00, 0.0
The ratio is preferably less than 65: 1.00, 0.060: 1.00, 0.055: 1.00, more preferably the latter order. And for paint coating applications, this nickel: phosphoric acid ratio
Less than 0.050: 1.00, 0.045: 1.00, 0.040: 1.00, 0.035: 1.00 is desirable, and the case of the latter order is more preferred.

The treatment liquid of the present invention preferably contains at least one of the following. (I) free or bound hydroxylamine, (ii) iron cation. The iron cation is preferably mainly a divalent cation because the phosphate of the divalent cation has a higher solubility in water than the phosphate of the trivalent cation. Various iron salts and iron oxides, and metallic iron itself (which generates and dissolves hydrogen gas in an acidic solution) can be used as a source. Ferrous sulfate is readily available and economical.

The ratio of the iron cation concentration g / L to the equivalent of orthophosphoric acid to the phosphate ion concentration represented by g / L 0.0003: 1.00, 0.0005: 1.00, 0.0007: 1.00, 0.0010: 1.
00,0.0015: 1.00, 0.0020: 1.00, 0.0025: 1.00, 0.0029:
1.00, 0.0032: 1.00 or more is preferable, and the case of the latter order is more preferable. Also, 0.010: 1.00, 0.008: 1.00,
0.006: 1.00, 0.0055: 1.00, 0.0050: 1.00, 0.0045: 1.00,
It is preferably less than 0.0040: 1.00 and 0.0035: 1.00, and more preferably the order of the latter.

In place of the iron cation, hydroxylamine is likewise preferred. Hydroxylamine is also stable when used as a salt with a strong acid. Oxime is a preferred source of hydroxylamine. Sulfates of hydroxylamine are most economically preferred. Sulfate has a large storage capacity as a concentrated solution of the treatment liquid of the present invention. The ratio of the concentration of hydroxylamine expressed in g / L of equivalents of hydroxylamine to the concentration of phosphate ions expressed in g / l of equivalents of orthophosphoric acid in the treatment liquid of the present invention is 0.00
10: 1.00, 0.0020: 1.00, 0.0030: 1.00, 0.0040: 1.00, 0.
[0045] The ratio is preferably not more than 0045: 1.00, 0.0050: 1.00, 0.0054: 1.00, 0.0056: 1.00, and more preferably the order of later.
Also for economic reasons 0.08: 1.00, 0.05: 1.00, 0.03: 1.00,
0.01: 1.00, 0.0090: 1.00, 0.0080: 1.00, 0.0070: 1.00,
It is preferably less than 0.0065: 1.00, 0.0060: 1.00, 0.0058: 1.00, and more preferably the order of later.

The treatment solution of the present invention may further contain cations of cobalt, magnesium, calcium and copper which are preferred in ordinary phosphating solutions. The concentration of these divalent cations other than copper is preferably in the above-mentioned nickel content range. When copper is contained, the concentration is 3 to 3 parts per liter of processing solution.
It is preferable to contain 100, 6 to 75, and 13 to 30 milligrams, and it is more preferable that the order is later.

For the purpose of bonding with a sealant or an elastomer, the calcium cation is converted to its g / L
Are 0.007: 1.00, 0.010: 1.00, 0.015: 1.00, as the ratio of the equivalent of orthophosphoric acid to the concentration of phosphoric acid expressed in g / L.
0.020: 1.00, 0.025: 1.00, 0.030: 1.00, 0.035: 1.00, 0.
040: 1.00, 0.044: 1.00, 0.048: 1.00 or more is preferable, and the case of the later order is more preferable. However, from an economic point of view this ratio should be 0.30: 1.00, 0.020: 1.00, 0.15: 1.00, 0.
10: 1.00, 0.090: 1.00, 0.080: 1.00, 0.075: 1.00,0.070:
1.00, 0.065: 1.00, 0.060: 1.00, 0.055: 1.00, 0.050: 1.
It is preferably at most 00, more preferably the latter case.

As in the case of the normal phosphating method, when the metal material to be treated is a zinc-iron-based material or when it is electrochemically active to the same extent, it is not necessary to add a special reaction accelerator. However, when the metal material to be treated is iron-based, a reaction accelerator is preferred. However, the present invention is not essential because it is a method of drying in situ. The prior art describes suitable reaction accelerators. That is, the following can be used as a reaction accelerator. That is, 0.3 to 4 g / L chlorate ion, 0.01 to 0.2 g / L nitrite ion, 0.05 to 2 g / L
M-nitrobenzenesulfonate ion of L, 0.05 to
2 g / L m-nitrobenzoate ion, 0.05-2 g /
L nitrophenol, 0.005 to 0.15 g / L bound or free hydrogen peroxide, 0.1 to 10 g / L bound or free hydroxylamine, 0.1 to 10 g / L
g / L reducing sugar.

The treating solution of the present invention further contains an adhesion enhancer in addition to the above-mentioned ordinary phosphating solution. This adhesion enhancer can be selected from the following groups: (I)
Film-forming organics. (Ii) U.S. Patent 5891519, 529858
9, 5266410, 5068299, 5063089, a polymer of vinylphenol in which an aromatic ring of a vinylphenol polymer is substituted with an aminomethyl group (hereinafter abbreviated as aminophenolic polymer in the present specification). (Iii) inorganic oxides of silicon, aluminum, titanium and zirconium.

The above-mentioned film-forming organic substance in the present invention refers to an organic substance having all the following characteristics. -3 film-forming organics separated from other substances
Solid at 0 ° C. and normal pressure. 5% with solubility in water or excellent dispersibility
A uniform solution containing the above is obtained. The homogeneous aqueous solution containing free film-forming organic material -0.10Cm ³ or more volumes, when dried at 30 ° C. in a wall container having a vertical wall to the base in the base area of 1.0 cm ^2, based containers A continuous solid of the film-forming organic material is formed, and the continuous solid has sufficient bonding force to be completely retained against gravity even when removed from the container.

When forming a phosphate film for paint, the film-forming organic substance used in the present invention is a monomer having acrylic acid, methacrylic acid, acrylate,
It can be selected from synthetic polymers selected from methacrylic esters, acrylamides, methacrylamides, acrylonitriles, and methacrylonitriles. Hereinafter, this is abbreviated as an acrylic polymer in the present invention.

The acrylic polymer used as an adhesion enhancer in the present invention further has a _T300 value of 0, 5, 10, 15, 20,
The temperature is preferably 25, 29, or 32 ° C. or more, and more preferably the order of later. In addition, the temperature is preferably 100, 75, 60, 50, 45, 41, 37, or 34 ° C. or lower, and more preferably the order of later. The T ₃₀₀ value and is,
The highest temperature at which a polymer air-dried film exhibits a twist coefficient of 300 kg / cm ² or more.

When a coating for paint is formed in the present invention, when a film-forming organic substance or an amino-phenolic polymer is contained, the concentration of these adhesion enhancers is g / L (in terms of solids after drying). Is 0.10: 1.00, 0.30: 1.00, 0.50: 1.00, 0.60: 1.00, 0.6 with respect to the phosphoric acid concentration g / L expressed in g / L of orthophosphoric acid equivalent.
5: 1.00, 0.70: 1.00, 0.75: 1.00, 0.80: 1.00 or more is desirable, and the case of the later order is more desirable. 5: 1.00, 3.0: 1.00, 2.5: 1.00, 2.0: 1.00, 1.5: 1.00,
1.2: 1.00 or less is preferable, and the case of the latter order is more preferable. In the case of a film-forming organic substance, the ratio is preferably 1.0: 1.00 or less.

The aminophenolic polymer added to the treatment solution when forming a coating for paint in the present invention preferably has at least one of the following characteristics. It is more preferable to have a plurality or all of the following characteristics.

All the substituents of the aromatic ring are substituted with aminomethyl groups, and all of the oxygen atom substituents directly connected to the aromatic ring are substituted with hydrogen, and the resulting polymer is a vinylphenol polymer And more preferably a 4-vinylphenol polymer having an average molecular weight of 300, 400, 500, 600, 700, 8
It is more preferable that the order of 00, 900, 1000 or more is more preferable, and the average molecular weight is 20,000,
15,000, 10,000, 9,000,8,000, 7,000, 6,000, 5,000,
The following order of up to 4,000, 3,000, 2,000 is even more preferred: the nitrogen atom of the aminomethyl substituent is each linked to three separate carbon atoms, ie the amino group is tertiary; rather than is amine oxide amino groups, - at least one component is linked to the nitrogen atom of the substituted aminomethyl _{group, -CH 2 - (CHOH) n} -CH 2 O
H is a polyhydroxyalkyl component represented by the general formula. In the above, n is a positive integer, and n ′ is the number of hydroxyl groups in all substituted aminomethyl groups in the amino-phenolic polymer, relative to the number of nitrogen atoms in all aminomethyl substituents in the aminophenolic polymer. The ratio is preferably 1.0, 2.0, 3.0, 4.0, 4.5, 4.9 or more, more preferably the order of later, and 11, 9.0,
It is preferably less than 8.0, 7.5, 7.0, 6.5, 6.0, 5.5, 5.1, and more preferably the latter case. At least one component linked to the nitrogen atom of the aminomethyl substituent in the aromatic ring is an unsubstituted alkyl group having no more than 4, 3, 2, 1 carbon atoms, and More preferred.

Of the inorganic adhesion enhancers, silica is most preferred. That is, silica in which particles of an appropriate size are stably dispersed can be easily obtained. When the adhesion enhancer is inorganic, its concentration is equivalent to the equivalent of orthophosphoric acid g /.
The ratio to the phosphate ion concentration represented by L is 0.003:
1.00, 0.005: 1.00, 0.007: 1.00, 0.009: 1.00, 0.011: 1.
The number is preferably 0, 0.013: 1.00, 0.015: 1.00 or more, and more preferably the order of later. 1.00: 1.00, 0.80: 1.00, 0.70: 1.00, 0.60: 1.00, 0.5 from economic point of view
0: 1.00, 0.45: 1.00, 0.43: 1.00, 0.41: 1.00, 0.39: 1.0
0, 0.37: preferably less than 1.00, and more preferably the order of later.

When the treating agent of the present invention is used as a film for joining an elastomer, the adhesion reinforcing agent is preferably an aminophenolic polymer rather than an acrylate polymer or an inorganic agent. When using this aminophenolic polymer, the ratio of the concentration of solid content after drying, expressed in g / L, to the concentration of phosphate ions, expressed in equivalent g / L of orthophosphoric acid, is 0.0005: 1.00, 0.0010: 1.00, 0.0020: 1.00,
0.0024: 1.00, 0.0027: 1.00, 0.0030: 1.00, 0.0032: 1.0
0, 0.0034: 1.00, 0.0036: 1.00, 0.0038: 1.00 or more are preferable, and the case of the latter order is more preferable. 5: 1.00, 3.0: 1.00, 1.0: 1.00, 0.50: 1.00, 0.25: 1 from an economic point of view.
00, 0.10: 1.00, 0.050: 1.00, 0.020: 1.00, 0.015: 1.00,
0.010: 1.00, 0.0090: 1.00, 0.008: 1.00, 0.0070: 1.00,
0.0060: 1.00, 0.0050: 1.00, 0.0045: 1.00, 0.0042: 1.0
It is preferably less than 0, 0.0040: 1.00, and more preferably the latter order.

The aminophenolic polymer added to the treatment liquid of the present invention when used as a film for bonding an elastomer preferably has at least one of the following characteristics. It is more preferable to have a plurality or all of the following characteristics.

All of the substituents of the aromatic ring are substituted with aminomethyl groups, and all of the oxygen atom substituents directly connected to the aromatic ring are substituted with hydrogen, and the resulting polymer is a vinylphenol polymer; More preferably, it is a 4-vinylphenol polymer having an average molecular weight of 300, 400, 500, 600, 700, 800, 900, 10
00 or more is preferable, and the case of the latter order is more preferable.
0,000,15,000, 10,000, 9,000, 8,000, 7,000, 6000, 5
Preferably no more than 000, 4000, 3000, 2000, more preferably the latter order, the nitrogen atom of the aminomethyl group substituted on the aromatic ring of the polymer molecule being bonded to three separate carbon atoms That is, the amino group is not an amine oxide but a tertiary amino group;-at least one substituent linked to the nitrogen atom of the aminomethyl substituent of the aromatic ring is preferably a monohydroxyalkyl group; Is at least 2 and 6,4,3,2 or less; at least one component linked to the nitrogen atom of the aminomethyl substituent of the aromatic ring is an unsubstituted alkyl group having a carbon number of 4, 3, 2, and 1.

The present invention is carried out by a drying method as it is.
That is, a layer of the treatment liquid of the present invention is formed on the surface of the metal material, and then the layer of the treatment liquid is dried without being washed away with water. Therefore, all the non-volatile substances in the treatment liquid layer chemically react with the surface of the metal material and remain at that location.

The treatment liquid of the present invention is placed on the surface of a metal material and then dried. This can be done by various methods performed by those skilled in the art. That is, for example, as a method of disposing the treatment liquid on the surface of the metal material, a method of immersing the metal material in the treatment liquid in the container, a method of spraying the metal material on the surface, and a method in which the lower roll of the metal material is placed in the treatment liquid It can be carried out by a method such as passing between the upper roll and the lower roll that are immersed. When the treatment liquid of the present invention is excessively present on the metal surface, the excess can be removed before drying by a dropping method using gravity, a squeezing method, a roll method, or the like. Drying can also be performed by a usual method, for example, by blowing hot air, passing through a heating oven, or heating by infrared rays.

When the metal material is smooth or continuous like a thin plate or a coil, it is preferable to use a commonly used roller set after drying. The temperature at the time of use of the treatment liquid may be within a range in which the treatment liquid is kept in a liquid state, and room temperature, that is, 20 to 30 ° C. is simple and economical for roller coating. When the metal material is a coil, rapid treatment is desirable, and in such a case, it is preferable to use infrared radiation for drying.
The temperature is preferably 0, 30, 40, 50, 60, 66 ° C. or higher, and more preferably the order of the latter. 230, 220, 210, 200, 190, 180,
The temperature is preferably lower than 177 ° C., more preferably the latter case.

When forming a film for bonding the elastomer, the heating temperature of the metal material is 150, 125, 120, 115, 105,
The temperature is more preferably lower than 95 ° C., more preferably the order of the latter. The temperature of the metal material may be the same when the heating is performed by another method, for example, by blowing hot air.

When the metal material to be treated has a shape unsuitable for roll coating, the treatment liquid of the present invention may be sprayed on the surface of the metal material. At this time, the metal material may be preheated. After that, it is dried as it is. Such a method may be repeated until the film has a desired thickness. The drying temperature of the metal material may be as described above.

The weight of the dry additive per unit area formed on the surface of the metal material (usually called the film weight) is
0.05, 0.10, 0.15, 0.20, 0.24, 0.26, 0.28, 0.30, 0.
It is preferably at least 32 g / m ^2, more preferably the order of the latter. In the case of forming a film for bonding the elastomer, it is preferably at least 0.35, 0.40, 0.45, 0.50, 0.53 g / m ^2, more preferably the order of later. However, from an economic point of view, the film weight is 8.6, 5.0, 4.0, 3.5, 3.0,
It is preferably less than 2.5, 2.0, 1.5, 1.2 g / m ^2, more preferably the latter order. Also, when forming a coating film to be painted, if another conversion coating is formed after the metal material is further processed, the coating weight is 1.00, 0.90, 0.85,
It is preferably less than g / m ^2, more preferably the order of the latter.

The metal material to be treated is preferably washed first to remove dirt, organic dirt, other metal powders and impurities. This cleaning may be performed by a known method performed by those skilled in the art for the metal material. That is, for example, a galvanized steel sheet is cleaned using a normal hot alkali cleaning agent, rinsed with warm water, squeezed, and dried. For aluminum, first rinse with a normal alkaline cleaner, rinse with warm water, then rinse with neutralizing acid,
Thereafter, the present invention may be implemented.

[0044]

EXAMPLES (Group 1) In this example, two types of concentrated solutions were used as known phosphating solution components. These were prepared by mixing an adhesion enhancer with them. Other components were used as needed. The composition of the two types of phosphating solutions is shown in Table 1
C and 2C. In this table, the valence of H ₃ PO ₄ is all pentavalent phosphorus in chemical equivalents. Unlisted balance is deionized water.

Processing solutions were prepared as shown in Table 2. Capacity 10
The balance for 0 milliliters (ml) is distilled water. The poly (acrylic acid) solution in Table 2 is Rohm & Haas C
o., ACCUMER ^TR 1510 poly (acrylic acid) solution, reported by the manufacturer to be a colloidal aqueous solution of poly (acrylic acid) with a molecular weight of about 6 × 10 ⁴ and a polymer solids concentration of 25%. The amino-phenolic polymer solutions in Table 2 were made based on Example 7 of US Pat. No. 5,891,952.
The polyacrylate latex in Table 2 is Rohm & Haas C
. o, made of glass RHOPLEX ^TM HA-16 acrylic binder solid concentration of the polymer in the T ₃₀₀ value is 33 ° C. The manufacturer reports have nonionic is 45.5 percent self - cross-linking acrylic polymer It is a dispersion. The colloidal silica dispersion in Table 2 is CABO manufactured by Cabot Corp.
SPERSE A-205, containing 12% solids as reported by the manufacturer.

All of the treatment liquids in Table 2 were applied to commercially available test panels made of hot-dip galvanized steel sheet in order to make the coating amount uniform.
The coating was performed using a # 3 Draw Bar, and after coating, the coating was dried in situ at the drying temperatures described in Tables 3 and 4. The coating amount in Tables 3 and 4 was determined by first rubbing the coated panel with a cloth impregnated with methyl ethyl ketone, drying and weighing, then rubbing twice with an ammonium dichromate solution, washing with water, drying and weighing. The weight difference between the two weighings is the total coating weight, and this was divided by the coating area to obtain the coating weight.

The panel surface of the clean phosphate film formed by drying as it was was coated with an AKZO ^™ 9 _× 444 primer and a polyester top coat that did not crack or peel even in a 2T bending test. Each of these panels was subjected to the ASTM-D4145 OT, IT, 2T bending test. The results are shown in the bending test results in Tables 3 and 4. In the table, 1 is a pass in IT but OT is rejected, 2 is a case where OT and IT are rejected but 2T is passed, and F is a case where 2T is rejected (however, even if F, Not necessarily a commercial reject panel).

In addition to the above, the following processing solutions were prepared. That is, equal amounts of the following (i), (ii), (iii) and (iv) were mixed.
(I) Table 1 ^{2C, (ii) RHOPLEX TM HA} -16 acrylic binder, (iii) 75% of aqueous H ₃ PO _4, (iv) deionized water. More deionized water was added and the volume of this mixture was 11%
Was prepared. This treatment liquid was used in the same manner as described in Tables 2, 3 and 4. However, # 12 was used instead of # 3 Draw Bar, and the drying temperature in Tables 3 and 4 was 218 ° C. After that panel is subjected to a primer of AKZO ^TM PMYO154, it was subjected to a top coat of AKZO ^TM FLUOPON ^TM. The painted panel passed OT bending and had excellent adhesion.

[0049]

[Table 1]

[0050]

[Table 2]

[0051]

[Table 3]

[0052]

[Table 4]

[0053]

[Table 5]

[0054]

[Table 6]

[0055]

[Table 7]

(Group 2) Table 5 shows the components of the phosphating solution used in this group. In the table, the nickel dehydrogen phosphate solution contains 8.2% of Ni ²⁺ ,
It contains 37.6% of PO ₄ ^3- . Table 6 shows the components of the processing solutions of the examples of the present invention and the processing solutions of the comparative examples.

The amino-phenolic resin polymer solution PS1 in Table 6 is described in US Pat. No. 5,068,299, column 11, columns 45-59.
Created in a row manner. However, the proportions of the components were as described below. Propasol ^TM P propoxylated propane solvent:
241 parts, Resin M: 109 parts, N-methylglucamin: 179 parts mixed with deionized water 272 parts, 37% formaldehyde solution: 74 parts, and the final solution was diluted with deionized water to a solid content of 30 parts. % Brought the pH to 9.8 ± 0.2.

The amino-phenolic resin polymer solution PS2 in Table 6 was prepared according to Example 3 of US Pat. No. 5,891,592.

The amino-phenolic resin polymer solution PS3 in Table 6 was prepared based on Example 1 of US Pat. No. 5,891,592. However, the proportions of the components were as described below. First stage deionized water: 318 parts, sodium hydroxide: 4.2 parts,
N-methyl ethanolamin: 29 parts, poly (4-hydroxys
tyrene): 48 parts, paraformaldehyde: 12.5
Parts, deionized water in the second stage: 349 parts, 75% aqueous phosphoric acid: 30 parts, 60% fluorotitanic acid: 3.0 parts,
Third stage deionized water: 31 parts and the final solution has a pH of 5.0 and a non-volatile content after drying of 10.6%.

By coating each of the treatment solutions of Examples and Comparative Examples in Table 6 on the surface of a galvanized steel sheet (Galvaneal ^™ ), a phosphate film of 0.54 to 1.8 g / m ² was dried in a dry state. Formed. Drying as it is, maximum temperature 66-93
C. After cooling, the dried surface of each specimen
AT ^R 06-1245 (Henkel Cop.Henkel Surface Technologi-
es Div. Oak Creek, Wisconsin) and baked according to the manufacturer's instructions. The force required to peel the baked sealant from the surface of the test material was measured. The results are shown in the adhesion strength in Table 7.

Continued on the front page F term (reference) 4D075 BB24X BB75X BB93X CA13 4K026 AA02 AA07 AA13 AA22 BA04 BB06 BB08 CA18 CA23 CA26 CA38 CA39 CA41 DA11 DA13 EB08

Claims (20)

[Claims] A phosphoric acid treatment solution for a galvanized steel sheet, comprising the following components, characterized in that it is dried and finished as it is without performing washing for removing the treatment solution. Salt treatment solution. A phosphate ion of 1.0 to 400 g / L in terms of the chemical equivalent of orthophosphoric acid; and a content of zinc cation of g / L in terms of the phosphate ion content of g / L in the chemical equivalent of orthophosphoric acid. 0 in ratio.
003: 1.0 to 0.10: 1.00, one or more adhesion enhancers selected from the following: (i) an organic film-forming substance (ii) an aminophenolic polymer (iii) selected from silicon, aluminum, titanium, and zirconium Elemental inorganic oxide. 2. A phosphating solution according to claim 1, wherein the adhesion enhancer is selected from the following: acrylic acid, methacrylic acid and acrylic acid, salts of methacrylic acid, amides, esters and The content of the film-forming organic material, which is a polymer of a monomer selected from nitriles, in g / L is 0.10: 1.00-3 in the ratio of the phosphate ion content g / L in the chemical equivalent of orthophosphoric acid. .
0: 1.00, the aminophenolic polymer having a content g / L of:
0.10: 1.00 to 3.0: 1.00 in terms of the phosphate ion content g / L in terms of the chemical equivalent of orthophosphoric acid, the colloidal oxide of silicon, aluminum, titanium and zirconium The content g / L is 0.1 in a ratio to the phosphate ion content g / L in the chemical equivalent of orthophosphoric acid.
011: 1.00 to 0.70: 1.00. 3. The phosphating solution according to claim 2, further comprising one or more of the following components: g / L of manganese cation, chemical equivalent of orthophosphoric acid. In the ratio to the phosphate ion content g / L
30: 1.00 to 0.3: 1.00, the nickel cation having a g / L ratio of 0.0 to the phosphate ion content g / L in terms of the chemical equivalent of orthophosphoric acid.
07: 1.00 to 0.070: 1.00, and at least one of the following (i) and (ii). (i) The hydroxylamine source is defined as the ratio of the chemical equivalent of hydroxylamine, g / L, to that of orthophosphoric acid, relative to the phosphate ion content, g / L, of 0.0030: 1.00 to 1.00.
0.03: 1.00, (ii) The iron cation has a g / L of 0.00 in terms of the phosphate ion content g / L in the chemical equivalent of orthophosphoric acid.
07: 1.00 to 0.010: 1.00. 4. The phosphating solution according to claim 3, which comprises any of the following components in the following range: g / L of calcium cation is equivalent to phosphate ion in a chemical equivalent of orthophosphoric acid. The ratio to the content g / L is 0.
030: 1.00 to 0.080: 1.00, the aminophenolic polymer is 0.0020: 1 in a ratio of g / L to the phosphate ion content g / L in the chemical equivalent of orthophosphoric acid. 0.0 to 0.020: 1.00, the zinc cation having a g / L ratio of 0.001 in terms of the phosphate ion content g / L in the chemical equivalent of orthophosphoric acid.
5: 1.0 to 0.035: 1.00, the manganese cation having a g / L ratio of 0.0 to the phosphate ion content g / L in terms of the chemical equivalent of orthophosphoric acid.
50: 1.00 to 0.15: 1.00, the nickel cation having a g / L of 0.0 in terms of the phosphate ion content g / L in the chemical equivalent of orthophosphoric acid.
20: 1.00 or more-The aminophenolic polymer having all of the following properties:-The substituent of the aromatic ring is substituted with an aminomethyl group, and the oxygen atom directly connected to the aromatic ring All of the substituents are substituted with hydrogen, and the resulting polymer is a vinylphenol polymer having an average molecular weight of 300 to 10,000. -The nitrogen atom of the aminomethyl substituent is linked to three separate carbon atoms and is not an amine oxide. -At least one component linked to the nitrogen atom of the substituted aminomethyl group is a hydroxyalkyl group having 2 to 6 carbon atoms. -At least one component linked to the nitrogen atom of the substituted aminomethyl group is an unsubstituted alkyl group having less than 3 carbon atoms. 5. The phosphating solution according to claim 3, which contains any of the following components in the following range: the acrylic polymer has a content of g / L of phosphorus in a chemical equivalent of orthophosphoric acid. 0.000020: 1.0 to 0.020: 1.00-The ratio of the zinc cation to the g / L of the acid ion is g / L, and the content of g / L is the phosphate ion in the chemical equivalent of orthophosphoric acid. With respect to the content g / L of
0.015: 1.0-0.06: 1.00-The manganese cation has a content g / L of 0.050 in terms of the phosphate ion content g / L in the chemical equivalent of orthophosphoric acid. : 1.00 to 0.15: 1.00-The nickel cation content is 0.020: 1.g / L in the ratio of the phosphate ion content g / L in the chemical equivalent of orthophosphoric acid. 00 or more-the acrylic polymer with all the following characteristics:-the acrylic polymer separated from other substances is 3
Solid at 0 ° C. and normal pressure. -5 with water solubility or excellent dispersibility
% Or more. -When a uniform aqueous solution containing an acrylic polymer in a volume of 0.10 cm ³ or more is dried at 30 ° C. in a wall container having a base area of 1.0 cm ² and a wall perpendicular to the base, the base of the container becomes A continuous solid of acrylic polymer is formed, which has sufficient bonding strength to be completely retained against gravity when removed from the container. -T ₃₀₀ value between 15 and 50 ° C. 6. A method for forming a paint coating on a surface of a metal material, comprising the following steps: (i) forming a phosphating solution layer according to claim 5 on a surface of a metal material; Process. (ii) A step of forming a phosphate film on the surface of the metal material by drying and finishing without performing intermediate washing for removing the phosphating solution of (i) from the surface of the metal material. (iii) a step of applying paint to the dried phosphate film. 7. The method for forming a paint coating on a surface of a metal material according to claim 6, wherein the step (i) is performed in a temperature range of 20 to 30 ° C., and the step (ii) is performed at a maximum temperature of 180 ° C. or lower. 8. The method of claim 6, wherein the weight of the phosphate coating formed at the end of step (ii) is from 0.20 to 1.00 g / m ² . 9. A method for forming an elastomer coating on a surface of a metal material, comprising the steps of: (i) forming the phosphating solution layer according to claim 4 on the surface of the metal material; (ii) A step of forming a phosphate film on the surface of the metal material by drying and finishing without performing intermediate washing for removing the phosphating solution of (i) from the surface of the metal material. (iii) a step of applying an elastomer to the dried phosphate film. 10. The method for forming an elastomer coating on a surface of a metal material according to claim 9, wherein the step (i) is performed in a temperature range of 20 to 30 ° C., and the step (ii) is performed at a maximum temperature of 105 ° C. or less. 11. A method for forming an elastomeric coating on a surface of a metallic material according to claim 10, wherein the phosphate film formed at the end of step (ii) has a weight of 0.45 to 2.0 g / m ^2. . 12. A method comprising the following steps:
A method of forming a phosphate film on the surface of a metal material. (i) a step of forming the phosphating liquid layer according to claim 3 on a surface of the metal material; (ii) a step of forming a phosphate film on the surface of the metal material by drying and finishing without performing intermediate washing for removing the phosphating solution of (i) from the surface of the metal material; 13. The step of forming a phosphate film on the surface of the metal material according to claim 12, wherein the step (i) is performed in a temperature range of 20 to 30 ° C., and the step (ii) is performed at a maximum temperature of 230 ° C. or less. Method. 14. The phosphate film formed at the end of step (ii) weighs 0.05 to 8 g / m ^2.
A method of forming a phosphate film on the surface of a metallic material. 15. A method comprising the following steps:
A method of forming a phosphate film on the surface of a metal material. (i) a step of forming the phosphating liquid layer according to claim 2 on the surface of the metal material; (ii) A step of forming a phosphate film on the surface of the metal material by drying and finishing without performing intermediate washing for removing the phosphating solution of the above (i) from the surface of the metal material. 16. The method according to claim 15, wherein the step (i) is performed in a temperature range of 20 to 30 ° C., and the step (ii) is performed at a maximum temperature of 230 ° C. or less. Method. 17. The phosphate coating formed at the end of step (ii) weighs 0.05 to 8 g / m ^2.
A method of forming a phosphate film on the surface of a metallic material. 18. A method comprising the steps of:
A method of forming a phosphate film on the surface of a metal material. (i) a step of forming the phosphating liquid layer according to claim 1 on a surface of a metal material; (ii) A step of forming a phosphate film on the surface of the metal material by drying and finishing without performing intermediate washing for removing the phosphating solution of (i) from the surface of the metal material. 19. The method according to claim 18, wherein the step (i) is performed in a temperature range of 20 to 30 ° C. and the step (ii) is performed at a maximum temperature of 230 ° C. or less. Method. 20. The method of claim 18, wherein the weight of the phosphate coating formed at the end of step (ii) is 0.05 to 8 g / m ² .