JPH07166126A - Production of polyfunctional water glass coating material - Google Patents

Abstract

PURPOSE:To produce a new non-toxic coating material having an antifouling function in combination with a rustproofing function and free from environmental pollution by adding a specified filler to a (denatured) water glass vehicle which is prepared by a specified method. CONSTITUTION:Polyethylene glycol or polypropylene glycol (polymerization degree is 2 to 2000) having functional groups is initially added to a solution of a silicate of the formula [M is K, Na, etc.; (n) is 2 to 31 and the resultant mixture is reacted to obtain an elastic get (PSE) having a high silicate content. The obtained PSE is then dissolved in a solution of a silicate of the formula [provided that (n) is 3 to 51 so that the weight ratio of PSE/SiO2 may be 0.1 to 100. An aluminium compound such as aluminium sulfate is subsequently added thereto so as to have 0.05 to 5 molar ratio of Al2O3/SiO2 and the resultant mixture is then heated and denatured at 30 to 100 deg.C to obtain a silicate colloid vehicle. A filler selected from an ion-exchange alumosilicate, powdery Zn, powdery Al, a fine powder of their alloy, an alkaline earth metal and a metal oxide is then added to the vehicle and a pigment is subsequently added thereto.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to the production of a water glass-metal, alloy fine powder multifunctional coating which is an improvement of a completely inorganic anticorrosion and antifouling coating (Registration No. W092 / 10546 and 1993 Patent Application No. 65887). It is about the method.

A water glass colorant modified as a polysilicic acid compound includes zinc, aluminum metal, and alloy fine powder thereof and alkaline earth metal, and alumosilicate and oxide partially or wholly exchanged with rare earth metal ions. It is an inorganic coating composition in which one or two of the above are added as a dispersant.

[0003]

2. Description of the Related Art Inorganic paints using water glass are thermosetting paints (Australian Patents 104231 and 1937).
After being developed as a natural curing type with a chemical curing agent or post treatment.

The high-concentration zinc paint which is widely used as a heavy anticorrosion paint has a high zinc content of up to 91% and a high raw material cost.

As a curing agent for water glass paints, silicides,
Many patents using metal oxides, polyphosphates, metal powders, etc. are known, but the essential drawbacks of water glass-based paints, such as water resistance and rapid curing, have not been completely solved. However, there are limitations such as short working time before paint, and the drawbacks of low practicality have not been overcome.

On the other hand, a paint using a heavy metal ion-exchanged zeolite compound having a bactericidal action (Patent Application No. 2 of 1987)
No. 43665) and other water glass antifouling paints have been reported, but they utilize the bactericidal effect of sequential ion dissolution of heavy metals, and are the same in principle as heavy metal-containing organic antifouling paints. However, it does not fundamentally solve the environmental pollution problem and the long-term antifouling problem.

[0007] In recent years, self-polishing antifouling paints containing cuprous oxide in a copolymer of acrylic resin and tributyltin have been developed and actually used, but their effective antifouling period is limited and long-term use. In the case of, it is likely that dissolved compounds will accumulate in the ocean.

Conventional inorganic coatings based on water glass have been used together with organic polymer coatings as anticorrosion coatings for various structures and ships under the marine environment. Is still limited.

[0009]

DISCLOSURE OF THE INVENTION The present invention is based on a modified water glass colorant or water glass colorant and zinc, aluminum metal or an alloy fine powder thereof, and ion exchange alumosilicates or oxides, and non-toxic substances based on carbonic acid compounds. The present invention provides a pollution-free inorganic coating material having both antifouling and antirust functions at the same time.

Further, the present invention has good adhesion to the base material of metal, concrete, porcelain, glass, wood and the like, and has excellent properties such as long-term water resistance, weather resistance, nonflammability, heat resistance, mildew resistance and antistatic property. The present invention provides a method for producing a multifunctional inorganic coating material having

At the same time, the present invention extends the pre-painting work time and accelerates the natural curing speed.

[0012]

In order to achieve the above object, silicate M ₂ O.nSiO ₂ (M: K, Na, L
_{i, CH 3, C 2 H} 5, n: polyethylene glycol having a solution to functional groups 2.0 to 3.0), was added the reaction of polypropylene glycol compound (n = 2 to 2000), silicate content High elastic gel (hereinafter referred to as PSE)
With a PSE / SiO ₂ weight ratio of 0.1 to 1
Silicate M ₂ O.nSiO ₂ (M: K,
Na, Li, CH ₃ , C ₂ H ₅ , n: 3.0 to 5.0)
After being dissolved in the solution, Al ₂ O ₃ (or B ₂ O ₃ ) / S
An aluminum compound (aluminum sulfate, alum, aluminate) or borate is added so that the molar ratio of iO ₂ is 0.05 to 5.0, and the mixture is heat-denatured at 30 to 100 ° C. to form a silicate colloid. A colorant is obtained, and one kind of fine powder of aluminosilicate, zinc or aluminum exchanged with alkaline earth metal and transition metal ions or fine powder of their alloys and alkaline earth metal and metal oxide, and Two
More than one filler was added, and any pigment was added to it.

Further, in the coating composition according to claim 1, polyethylene glycol or polypropylene glycol compound (degree of polymerization n = 2 to 2000) is allowed to act on a silicate solution having a molar ratio of 0.25 to 0.4, pH 6.5-7.5
It is also possible to obtain a modified silicate elastic body close to neutrality.

Further, in the coating composition according to claims 1 and 2, according to claim 2, a solution of PSE / SiO _{2 in} a weight ratio of 1.0 to 10 has a molar ratio of Al ₂ O ₃ (or B ₂ O ₃ ) / SiO ₂ . An aluminum compound, a borate or the like may be added so that the ratio becomes 0.9 to 5.0 to obtain a color developing agent containing a polysilicic acid elastic material heat-modified at 30 to 100 ° C.

Also, in the paint according to claims 1, 2 and 3,
5 to 70% of zinc, aluminum or its alloy fine powder is added to the modified polysilicic acid elastomer color-developing agent, and the weight ratio of alumosilicate is 5 to 40%, rare earth metal oxide, barium sulfate, metal oxide. (ZnO, TiO ₂ , Cu ₂ O,
_{CuO, Fe 2 O 3, Fe} 3 O 4, MnO 2, Mn 3 O
₄ , Cr ₂ O ₃ , Al ₂ O ₃ ) and metal carbonates, SiO
You may make it obtain the multifunctional coating material which added ₂ , C, etc.

The silicate M ₂ O.nSiO ₂ (M:
_{K, Na, Li, CH 3} , C 2 H 5, n: 2.5~5.
The solution of 0) or a solution obtained by diluting it with water is used as a color-developing agent, while the solid dispersant according to claim 4 comprises one or two of the above aluminum compounds or borate. 00
1 to 1.0%, preferably 0.05 to 0.09% and n =
2-2000 polyethylene glycol or polypropylene glycol was uniformly mixed with 0.01 to 5% of the solid dispersant as a gel-forming agent and a curing agent to prepare a slurry pigment, and the above-mentioned color developing agent or the above-mentioned silicic acid was added thereto. It is also possible to add salt to form a two-component paint.

Further, in the paints according to claims 1, 2, 3, 4 and 5, the ship bottom having the pollution-free and anti-corrosion effect and the anti-corrosion effect which prevent adhesion of organisms adhering to ships by the physicochemical characteristics of the coating film. I got a paint for it.

Further, in the paints according to claims 1, 2, 3, 4, 5 and 6, iron, iron alloy, wood, concrete, slate, as a multi-functional paint of water glass 1 liquid 1 solid phase type and 2 liquid type, It can be used for glass and linen.

[0019]

In order to achieve the above-mentioned object, a coating of water-glass binder and the above-mentioned metal compound and aluminosilicate is formed with a fine pore mechanism having ion exchange and adsorption properties, solid acidity and electrostatic effect. Let

The primary modification of water glass is the functionalized polyethylene glycol or polypropylene glycol (n
= 2 to 2000)), which is a polysilicic acid elastic gel synthesis with a low alkali content.

The degree of gelation of water glass and the viscosity of silicic acid gel are related to the silicic acid ratio and concentration of water glass. 3 Obtaining a gel with water glass having a silicic acid ratio of 3 or less is advantageous in terms of obtaining a gel with high activity, but a higher silicic acid ratio decreases the gel production amount, resulting in the consumption of additives used for modification. Since the amount is large, it is preferable that the silicic acid ratio is 2.4 to 2.5%.

The amount of the additive used for the modification is preferably 30 to 40% so that the gel production amount becomes constant.

In the secondary modification of water glass, the primary modified elastic gel is dissolved in water glass having a silicic acid ratio of 3 or more to form a color-developing agent having a high silicic acid content, elasticity and strong adhesion. It is a process.

In this case, it is preferable to adjust the weight ratio of PSE / SiO ₂ to 0.1 to 100, preferably 0.1 to 10. When it is less than 0.1, the modifying effect is small, and when it is 100 or more, the stability of the system and the physical properties of the coating deteriorate.

The third modification is a modification process with an aluminum compound and a borate. The modification with the aluminum compound and the borate is to stop the hardening of the coating and obtain a modified color-developing agent having a quasi-zeolitic structural material.

In this case, Al ₂ O ₃ (or B ₂ O ₃ ) /
The molar ratio of SiO ₂ is 0.05 to 0.2, preferably 0.
It is better to set it to 08 to 0.12. When it is less than 0.05, there is no denaturing effect, and when it is more than 0.2, the stability of the system is lost and workability is poor.

Zinc and aluminum fine powders added to the color spreader as solid dispersants, their alloy fine powders and inorganic compounds are 5 to 70% and 30 to 95%, respectively, in the solid dispersant, and they are paint films. It plays the role of maintaining the multifunctionality of the coating, including the acceleration and completion of curing, the rust prevention function and the antifouling function.

On the other hand, without using the modified silicate color-developing agent, water glass was used as it is as a color-developing agent, and polyethylene glycol or polypropylene glycol and an aluminum compound or borate were added to the solid dispersant in the same ratio as in the above-mentioned method to form a slurry. The same two-component paint can be used as the same paint.

The inorganic coating containing the fine metal powder controls the iron surface electrode reaction, while adsorbing and fixing oxygen to reduce the oxygen concentration supplied to the electrochemical anodic reaction on the iron surface.
It is believed that it exerts a comprehensive effect such as ion exchange and adsorption, electrostatic field and solid acidity, surface pH adjustment, etc. to bring about a rust prevention and antifouling function.

The coating film has good cold resistance, impact resistance, and heat resistance,
Water adsorbed in fine pores does not freeze under normal conditions, and the specific resistance value of the coating film is 10 ⁸ Ω · cm or less, and the antistatic property is good, so dust adhesion and mold formation etc. Can be prevented. From the above results, this paint is a paint with durability such as salt moisture resistance, non-combustible heat resistance, corrosion resistance, antifouling, antistatic, etc., as a ship, marine structure, undersea equipment,
It can be used for sewage purification equipment, seawater ion exchange concentration equipment, and general equipment.

[0031]

Embodiments of the present invention will be described below with reference to the drawings.

(Example 1) Molar ratio (SiO ₂ / M ₂ O,
As for M, polyethylene glycol (n = 2) was added to a silicate solution in which Na, K, Li, CH ₃ , C ₂ H ₅ ) was 3.0 to obtain an elastic gel (PSE) having a high silicic acid content.

This elastic gel was mixed with a molar ratio (SiO ₂ / M ₂
O) is 4.0 to 4.5 and PSE / Si is added to the silicate solution.
After dissolving so that the weight ratio of O ₂ becomes 1.0, Al ₂
Potassium alum was added so that the O ₃ / SiO ₂ molar ratio was 0.08, and the mixture was heated and reacted at 100 ° C. to obtain a modified silicate colloid solution.

Example 2 A modified silicate colloidal solution was obtained in the same manner as in Example 1 so that the Al ₂ O ₃ / SiO ₂ molar ratio was 0.16.

(Example 3) A modified silicate colloidal solution was obtained in the same manner as in (Example 1) so that the Al ₂ O ₃ / SiO ₂ molar ratio was 0.24.

Example 4 Molar ratio (SiO ₂ / M ₂ O;
M was Na, K) and polypropylene glycol (n = 3 or more) was added to the silicate solution of 2.4 to 2.6 to obtain an elastic gel having a high silicic acid content.

This high silicic acid elastic gel was used in a molar ratio (SiO ₂ /
M ₂ O) in a silicate solution of 3.0 to 4.0 into PSE / Si
After melting so that the weight ratio of O ₂ is 10, Al ₂ O
Aluminum sulfate was added so that the molar ratio of ₃ / SiO ₂ was 0.24, and the mixture was heated and reacted at 100 ° C to obtain a modified silicate colloid solution.

Example 5 The modified silicate color-developing agent produced by the method of Example 1 was
An iron plate test piece (300 mm × 300 mm × 20 m) which was prepared by preparing a paint having a composition as shown in [Table 1] and surface-treating
m), and after drying for 2 days, a control test plate (PVC board,
The experiment was conducted by immersing it in the ocean for 1 year together with the paint of Company C).

[0039]

[Table 1]

As a result of the test, the following [Table 2a] and [Table 2]
b], [Table 2c] and [Table 2d] are shown as the results of the attached bioanalysis. As shown, it showed a superior antifouling and rustproof effect compared to the control area.

These tests show the results of immersion for 12 months, and the sampling date was November 2, 1992.
On day 0, the collection area is 30 cm x 30 cm.

[Table 2a], [Table 2b], [Table 2]
In c] and [Table 2d], the vinyl chloride board section is an untreated control section, + represents appearance, and the ship bottom paint is an existing self-polishing paint.

[0043]

[Table 2a]

[0044]

[Table 2b]

[0045]

[Table 2c]

[0046]

[Table 2d]

(Example 6) The modified silicate color-developing agent produced by the method of (Example 2) was mixed with a coating composition as shown in [Table 3], and the same method as in (Example 5) was used. I did an experiment. The film was cured for 1 day.

[0048]

[Table 3]

As a result of the test, no apparent change and no adhesion of marine organisms were observed.

(Example 7) To the modified silicate color-developing agent produced by the same method as in Example 3, the additives shown in [Table 4] were added to prepare a coating composition (Example 5). The experiment was conducted in the same way as. The curing time of the coating film was 2 days.

[0051]

[Table 4]

The results of the experiment are shown in (Example 5) and (Example 6).
It was exactly the same.

(Example 8) A paint composed of the compositions of (Example 5), (Example 6) and (Example 7) was used to paint the bottom and hull of a ship for two years of navigation. No adhesion was observed and no change was observed in appearance.

Physical properties of the coating films of (Example 5), (Example 6) and (Example 7) are as shown in [Table 5].

[0055]

[Table 5]

Example 9 Silicate M ₂ O.nSiO
₂ (M: K, Na, Li, n = 2.0 to 3.0) was diluted to 1/2 with water to obtain a color developing agent.

On the other hand, a solid dispersant was uniformly mixed in a composition as shown in [Table 6] to prepare a slurry pigment, which was mixed with the above-mentioned color developing agent at a ratio of 1: 1 to provide a coating material.

[0058]

[Table 6]

(Example 10) A solid dispersant having the composition shown in [Table 7] was prepared in the same manner as in Example 9, mixed with a color-developing agent at 0.9: 1.1 and provided as a coating material. did.

[0060]

[Table 7]

Example 11 A marine test was conducted by applying the paints of (Example 9) and (Example 10) to an iron plate sample (300 mm × 300 mm × 20 mm). The test results are [Table 8a], [Table 8b],
[Table 8c] and [Table 8d] show the results of the attached biological analysis. As can be seen from the test results, it can be seen that the antifouling and rust resistance is superior to the control group.

These tests show the immersion results for 12 months, and the sampling date was November 2, 1992.
On day 0, the collection area is 30 cm x 30 cm.

[Table 8a], [Table 8b], [Table 8]
In c] and [Table 8d], the PVC board section is an untreated control section, + represents appearance, and the ship bottom paint is an existing self-polishing paint.

[0064]

[Table 8a]

[0065]

[Table 8b]

[0066]

[Table 8c]

[0067]

[Table 8d]

[0068]

According to the present invention, it is possible to provide a new antifouling paint which is made of an inorganic compound which is fundamentally different from the conventional ship bottom paint and which also has a pollution-free rust preventive function.

This paint solves the antifouling problem not only in the ship department but also in the cooling water channels of power plants and marine structures. Also, the single paint fulfills the anticorrosion function and eliminates the trouble of undercoating and intermediate coating. At the same time, it also solves the pollution problem at the time of coating with an organic solvent.

Claims (7)

[Claims] 1. A silicate M ₂ O.nSiO ₂ (M: K, N
_{a, Li, CH 3, C} 2 H 5, n: 2.0~3.0 solution of polyethylene glycol having a functional group), polypropylene glycol compounds (n = 2 to 2000) was added the reaction, silicate-containing An elastic gel with a high amount (hereinafter referred to as PSE) is made, and the weight ratio of PSE / SiO ₂ is 0.1.
Silicate M ₂ O · nSiO ₂ (M:
_{K, Na, Li, CH 3} , C 2 H 5, n: 3.0~5.
0) After being dissolved in a solution, Al ₂ O ₃ (or B ₂ O ₃ )
Aluminum compound (aluminum sulfate, alum, aluminate) or borate is added so that the molar ratio of / SiO ₂ is 0.05 to 5.0, and heat denaturation is performed at 30 to 100 ° C. to obtain a silicate colloid. One of aluminosilicate, zinc or aluminum fine powder or an alloy fine powder thereof, and alkaline earth metal and metal oxide which are exchanged with an alkaline earth metal and a transition metal ion to obtain a color developing agent. And a method for producing a one-liquid one-solid-phase multifunctional water glass multifunctional coating material, which comprises adding two or more kinds of fillers and adding an arbitrary dye. 2. A paint according to claim 1, wherein the molar ratio is 0.25.
Polyethylene glycol and polypropylene glycol compound (degree of polymerization n = 2)
˜2000) is applied to obtain a modified silicate elastic body having a pH of 6.5 to 7.5 close to neutrality. 3. The coating composition according to claim 1 or ₂ , wherein the molar ratio of Al ₂ O ₃ (or B ₂ O ₃ ) / SiO _{2 to} the solution having a PSE / SiO ₂ weight ratio of 1.0 to 10 according to claim ₂ . The ratio is 0.
Manufacture of a water glass multifunctional coating characterized in that an aluminum compound or borate is added so as to be 9 to 5.0 to obtain a color-developing agent containing a poly (silicic acid) elastic body heat-modified at 30 to 100 ° C. Method. 4. The coating composition according to claim 1, 2 or 3, wherein 5 to 70% of zinc, aluminum or an alloy fine powder thereof is added to the modified polysilicic acid elastomer color-developing agent, and alumosilicate is added thereto in a weight ratio. 5-40%, rare earth metal oxides, sulfates Baryuumu, metal oxides _{(ZnO, TiO 2, Cu 2} O, Cu
O, Fe ₂ O ₃ , Fe ₃ O ₄ , MnO _{2, Mn 3} O ₄ ,
Cr ₂ O ₃ , Al ₂ O ₃ ) and metal carbonates, SiO ₂ ,
A method for producing a water glass multifunctional coating according to claim 1, 2 or 3, wherein a multifunctional coating containing 10 to 50% of C or the like is obtained. 5. A silicate M ₂ O.nSiO ₂ (M: K, N
a, Li, CH ₃ , C ₂ H ₅ , n: _{2.5 to} 5.0) or a solution obtained by diluting it with water is used as a color-developing agent, while the solid dispersant according to claim 4 has 0.001 of a color-developing agent using one or two kinds of aluminum compound or borate
1.0%, preferably 0.05 to 0.09% and n = 2
A polyethylene pigment or polypropylene glycol of 2000 was uniformly mixed with 0.01 to 5% of a solid dispersant as a gel-forming agent and a curing agent to prepare a slurry pigment, to which the above-mentioned color spreader or the above-mentioned silicate salt was added. In addition, a method for producing a water glass multifunctional coating, which is a two-component coating. 6. The ship bottom according to claim 1, 2, 3, 4 and 5, which has both a pollution-free and anti-fouling effect and a rust preventive effect for preventing adhesion of organisms adhering to ships due to the physicochemical characteristics of the coating film. A method for producing a water glass multifunctional coating, which comprises obtaining a coating for water. 7. A paint according to any one of claims 1, 2, 3, 4, 5 and 6, which is a multifunctional paint of water glass 1 liquid 1 solid phase type and 2 liquid type iron, iron alloy, wood, concrete, slate, A method for producing a water glass multifunctional coating, which is adapted to be used for glass and linen.