JPS61223062A - Emulsion reactive with metal - Google Patents

Abstract

PURPOSE:The titled emulsion which is easily reacted with the surface of a metal to form an organic film of coating which is unreleasable even if it is brought into contact with heat or solvents, obtained by blending an aqueous solution of a specific triazinedithiol compound with a slightly water-soluble or water-insoluble organic compound. CONSTITUTION:(A) 100g water is blended with (B) 0.01-20pts.wt. triazinedithiol shown by the formula (number of atoms of main chain of substituent group R is 8-36; at least one of M is compound consisting of H, Na, Li, K, Rb, and Cs), and (C) 0.01-20pts.wt. slightly water-soluble or water-insoluble organic compound (e.g., higher alcohol, etc.), to give the emulsion.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a completely novel reactive emulsion with metals used for surface treatment of metals.

(Prior art and its problems) Conventionally, methods for generating organic films on metal surfaces include:
The following methods are used: (1) dipping in a polymer solution, (2) dipping in polymer latex, and (3) applying paint with a brush.

These methods are practical because they can be performed with simple operations, but the organic film formed on the metal surface by the above methods is not linearly bonded at the interface with the metal.
They are easily peeled off by heat, solvents, etc., and do not have sufficient corrosion resistance.Furthermore, they have many problems, such as difficulty in controlling the thickness of the film and the tendency for the film to become uneven.

(Technical problem of the invention) The present invention can generate an organic film on a metal surface that easily reacts with the metal surface and does not peel off even when it comes into contact with heat or solvent, and the thickness of the film can be freely controlled. The purpose of this study is to propose a reactive emulsion for metal surface treatment that can be controlled.

(Technical means for solving the problem) In order to solve the problem h.2, the reactive emulsion that reacts with the metal surface according to the present invention is a triazine dithiol represented by the following general formula, which contains the main substituent R. The number of atoms in the chain is 8 to 3B, and at least one or two of M is H, Na
, Li, K, Rh, and Cs and an organic compound that is sparingly soluble or insoluble in water.

MS SM [1] (Example) Examples of the present invention will be described below.

The present invention relates to a reactive emulsion with a metal that is used for metal surface treatment in which an organic film is formed on the metal surface by a dipping method.

Regarding reactive emulsions, there has already been research by Matsumoto et al. (Kobunshi Saishu Vol. 291 (1883)), but these were obtained by modifying the particle surfaces of polymer emulsions, which is the purpose of the present invention. It does not have the effect of easily reacting with metal surfaces to form a strong bond.

The present inventors previously discovered that triazine dithiol compounds strongly react with many metal surfaces (Mori and Nakamura;
Journal of the Chemical Society of Japan, No. 6, p. 788 (1977), No. 1
1, No. 1, p. 1477 (1979)), when a sparingly soluble or insoluble organic compound is dropped into these aqueous solutions under vigorous stirring, a milky emulsion is obtained, and when a metal plate is immersed in this and then heat treated, it becomes heat resistant. It was discovered that an organic film with excellent solvent resistance was formed. That is, when a sparingly soluble or insoluble organic compound is dropped into an aqueous solution of a triazinedithiol compound under stirring, an emulsion containing the organic compound is formed inside the micelles, with the parent part of the triazinedithiol on the outside and the lipophilic part on the inside. can get. A metal, such as copper, is immersed in this. Then, the parent moiety of triazinedithiol, for example, -5Na, -9H groups, easily reacts with the metal or its oxide on the surface to form 2-9Cu, and the entire emulsion particle is chemically adsorbed onto the metal surface. In this state, some of the -5Na and -9H groups react to form -9Cu, but when this is heat-treated, -9H groups react to form -9H.
The Na and -9H groups themselves or these react with the organic compound to form a polymer film. Therefore, after heat treatment, an organic film with excellent heat resistance and oil resistance is formed. Emulsion films made of low-molecular compounds before heat treatment are highly soluble in organic solvents.

Next, a method for preparing a reactive emulsion and a method for treating metal surfaces will be described in detail.

The reactive emulsion is composed of three components: triazinedithiols, poorly soluble or insoluble organic compounds, and water. Triazine dithiols are represented by the general formula [1], and the number of atoms in the main chain of the substituent R is 8 or more and 36 or less,
and at least one of M is H, Na, Li%, Rh.

It is a water-soluble compound consisting of Cs and the like. Specifically, R is -WHO, H,, -NHC,, H,, -NHC,
,H,i-NHC,,H,h ,-N(04H,)
, , -N(C,H12), %-N(Ct
x H2y), -N(CH□O)L, -WHO
) IXC'H,O.

-NH-O-CH, -NH-O-C/H, -5CrH,
7゜7I7 -SC, 2 stickers, -9C)I, CH(OH), 0HLO
COC, H, etc. can be increased. If the number of atoms in the main chain is less than 8, the stability of the emulsion produced will be extremely low, or no emulsion will be formed at all, and if it is more than 3C, the solubility of [l] will be markedly reduced, and a reemulsion will not be formed. It's hard to do.

The amount of (1) added depends on its solubility, but generally water 100%
0.01 to 20 parts by weight per g, preferably 0°1 to 5
Parts by weight.

MS SM 11) Slightly soluble and insoluble organic compounds include higher alcohols, higher fatty acids and their esters, vinyl compounds, paraffins,
Any compound that is liquid at 20℃ such as silicone oil, plasticizer, polyether, etc. is acceptable.The main ones are oleyl alcohol, undecyl alcohol, stearyl alcohol, dodecyl alcohol, linalool, Oleic acid, lyllonic acid, linoleic acid, stearic acid, allyl oleate, ethyl lylphate, octyl lylphate, allyl stearate, vinyl acetate, styrene, divinylbenzene, octyl acrylate, butyl acrylate, tetraethylene glycol dimethacrylate,
Examples include l,8-hexane diacrylate, dioctyl phthalate, linseed oil, soybean oil, dodecyl disulfide, polyethylene glycol octyl ether, WD-40, and Scherzol. The amount of these organic compounds added varies depending on the purpose, but is generally 0.0 g per 100 g of water.
The amount is 1 to 20 parts by weight, preferably 0.1 to 5 parts by weight.

However, in order to obtain a stable emulsion, there is a limit to the ratio of organic compound to triazine dithiol. This limit value cannot be determined because it differs depending on the type of triazinedithiol and the type of organic compound, but in many cases,
It is 0.1 part by weight or more.

To prepare a reactive emulsion, first, triazine dithiols are dissolved in 100 g of water, and an organic compound is slowly added dropwise while stirring. Although it is not necessary to specifically limit the stirring device or stirring speed, a more stable emulsion can be obtained by stirring at a relatively high speed using a simple device. Also, if necessary,
Stirring may be carried out at high temperatures (50-90°C).Additionally, a small amount of surfactant may be added to promote stabilization of the emulsion.

Although the reactive emulsion prepared as described above is stable for 24 hours or more, if left undisturbed, the emulsion may float to the surface of the liquid. However, if you try to shake it gently, it will quickly become a homogeneous emulsion. In this way a reactive emulsion is prepared.

The metals used in the present invention include copper and alloys thereof, nickel and alloys thereof, iron and alloys thereof, silver and alloys thereof, tin and alloys thereof, cobalt and alloys thereof,
It refers to plate-shaped, rod-shaped, wire-shaped, powder-shaped, and complex-shaped metal products made of metals such as zinc, aluminum, and their alloys, or their oxides. It is desirable that these be subjected to pretreatment such as degreasing and pickling prior to treatment, which is a common surface treatment for metals.

Typically, the above metals are added to these reactive emulsions.
Immerse at ~100°C for 1 second to 60 minutes. A long immersion at low temperatures and a short immersion at high temperatures is sufficient. After soaking, rinse lightly with water and drain in a centrifuge.
When heat treated by leaving it in a hot air oven at 0 to 200°C for 1 to 120 minutes, a metal product with an organic film formed on the surface can be obtained.

Next, an example of metal surface treatment using the above-described reactive emulsion will be described.

Example 1 0.4 g of triazinedithiol compound and 200 g of water were
00ml tall beaker, and stirred at 20℃ (Daiwa Labo Stara LD-08) while adding 1ml of organic compound.
11 was added dropwise from a pipette at a rate of 1/win. After 0 drops, stirring was continued for an additional 30 minutes, and the liquid changed from clear and colorless to milky, yielding a reactive emulsion. An acetone-degreased nickel plated plate (iron plate 80×30×lsm, plating thickness 2.51 L) is immersed in reactive emulsion 2001 heated to 80° C. for 5 minutes. After washing this with water and methanol, use a hot air dryer (Seiwa Riko DL) at 150°C.
S-45) for 15 minutes and heat treated. The results are shown in Table 1.

In the table, the film weight, degree of curing, feroxyl test, and degree of corrosion are as follows.

Film weight = (weight after heat treatment) - (weight before reactive emulsion treatment) Measurement of degree of cure: The sample after heat treatment was immersed in toluene for 24 hours.

Ferroxyl test: JIS H8617 corrosion rate constant: 200 ml of 3% Mail aqueous solution was taken, and the surface-treated sample was immersed in it at 40°C for 48 hours.

Corrosion degree; Corrosion loss (mg) / Area .0.

2.0 and 4.0 g were added dropwise at a rate of 1 ml/sin to prepare a reactive emulsion. A nickel plated plate was immersed in this at 80° C. for 5 minutes to perform surface treatment. Add this to water.
After washing with methanol, heat treatment was performed by heating at 150° C. for 15 minutes. The results are shown in Table 2.

Example 3 Dibutylaminotriazine dithiol monosodium 0
．． Put an aqueous solution consisting of 4 g and 200 g of water in a 3001 tall beaker, and add 2.0 μl of linseed oil to it.
A reactive emulsion is obtained by dropping the mixture at a rate of 1.5 in and stirring for an additional 30 minutes. A metal plate (80 x 30 x 1 ml) that has been degreased by A7T is immersed in this solution at 80°C for 5 minutes, and then washed with water and methanol. A sample was further heat-treated at 135° C. for 5 minutes. The results are shown in Table 3.

Table 3 Effect of the type of metal (effects of the present invention) As explained in detail above, the reactive emulsion with metal according to the present invention easily reacts with the metal surface and peels off even when it comes in contact with heat or solvent. It is possible to generate a strong organic film on the metal surface without any scratches, and the thickness of the film can also be freely controlled. The organic film formed on the metal surface by the above-mentioned reactive emulsion is heat infusible, solvent insoluble, and water resistant, so it is effective in preventing corrosion of metal. Furthermore, considering that corrosion protection of metals can be achieved by the very simple method of immersion, and that even complex shapes are possible, the ripple effect is immeasurable. Since it is expected to be highly resistant, it can also be used for adhesives, etc.

Claims (1)

[Claims] Among the triazine dithiols represented by the following general formula,
A compound in which the number of atoms in the main chain of the substituent R is 8 to 36 and at least one or two of M is H, Na, Li, K, Rb, or Cs is mixed with an organic compound that is sparingly soluble or insoluble in water. A reactive emulsion with a metal characterized by being obtained. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [1]