AU661923B2 - Water-glass, non-zinc multifunctional paint and its manufacturing method - Google Patents

Description

St

II

66923 Regutation 3.2

AUSTRALIA

Patents Act 1990 APPLICANT: KABUSHIKI KAISHA DAIEI KIKAI

NUMBER:

FILING DATE: Invention Title: WATER-GLASS, NON-ZINC MULTIFUNCTIONAL ITS MANUFACTURING METHOD PAINT AND The following statement is d full description of t his invention,, -including the best method of performing it known to me: ~t 4 C

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£4 L C

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2 "WATER-GLASS. NON-ZINC MULTIFUNCTIONAL PAINT AND ITS MANUFACTURING METHOD" The invention regards to water-glass, non-zinc multifunctional paint and its manufacturing method which concerns supplement and improvement of the complete inorganic anticorrosive, poisonless antifouling paint (Registration Number: W092/10546).

The paint is non-zinc inorganic paint wherein aluminosilicate and oxide partially or entirely ion-exchanged by alkaline earth metals and rare earth metal ions are added as dispersing agents to the water-glass vehicle denatured as a polysilicate compound.

The paint is micell-structured by ion exchanging, 1 absorbing and neutralizing effects of aluminosilicate after at 15 being applied, becomes a siloxane polymer sequentially crosslinked and produces a strong paint film with huge silicate molecules.

Said paint film has a special structure with micropores, an anticorrosive function which consists of absorption and 20 immobilization of oxide and inhibitation of iron ion current at- C I and a poisonless antifouling function which ionizes amino acid calcium colloid of marine deposits, and can be applied to the bottom of a ship and used as paint for marine Sstructure use or for decoration use.

The inorganic paint contains water-glass has been developed unexceptionally as non-zinc silicate paint which utilizes electrochemical cathodic protective effects of zinc after being first developed as a thermohardening paint L 3 (Australian patent No. 231 issued in 1937).

The raw material costs for the conventional highconcentration zinc silicate paints with up to 91 percent of zinc concentration is extremely high because it uses a large amount of zinc.

Also, it is difficult to co-ordinate colour tones due to a strong zinc colour.

Although many patented materials containing silicides, metal compounds, poly-phosphate, metal powder, etc. are known as hardening agents for water-glass paints, low practicality due to short work time prior to the painting work as well as low durability and slow hardenability which are water-glass paint's fundamental defects have not been improved thoroughly.

j 15 Some water-glass antifouling paints starting with the paints which utilizes heavy metal ionized zeolite compounds t- V have been reported. However, these paints utilize the bactericidal effect of sequentially ion dissolved heavy 1 metals and are theoretically the same as heavy metal i S 20 contained organic antifouling paints and do not solve :t drastically the problems with environmental contamination and ,L long-term antifouling property.

t 4 1- The conventional inorganic paints which use the waterglass as a base material has been used in conjunction with organic high molecular paints as anticorrosive paints for various structures under the marine environment and ships.

However, the extent of their use as multifunctional paints is still limited.

The invention was made to deal with the above-mentioned d i 1; i i 2.

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68 I4 4 circumstances and aims to provide a denatured water-glass vehicle and non-zinc, non-pollution inorganic paint wherein a poisonless antifouling function based on the ion exchange aluminosilicate is concurrent with an anticorrosive function.

The invention also aims to provide a multifunctional inorganic paint which is highly adhesive to base materials of concrete, porcelain, wood, etc. and has outstanding long-term waterproofness, weatherproofness, heatproofness, electrification resistance and bactericidal action.

Furthermore, the invention aims to longer the prepainting work time and enhance the natural hardening speed.

To solve these problems, the invention formed a micropore structured paint film with absorbency, solid 15 acidity and electrostatic efficiency as well as an ion exchange membrane containing an aluminosilicate that acts as a binder and filler for the water-glass.

The primary denaturation of water-glass is a polysilicate elastic composition wherein the amount of alkali is small due to the reaction with low molecular, low polymerized organic compounds including alcohol, aldehyde, ester, ether and amine, which have functional groups.

At this point, Na+s in the diffused layer are consumed, the polymerization of silicate negative ions and the potential of micelle decrease, denatured silicate gel deposits and the water containing sodium salt are freed.

The extent that water-glass is gelated and the viscosity of a silicate gel corresponds to the ratio and concentration of silicate within the water-glass.

Ic Cr 1 The generating process of gel in the reaction with polyethylene glycol water-glass is as shown in Figure 1.

As Figure 1 indicates, the lower the ratio and concentration of silicate within water-glass become, the lower the rate of gel generation becomes and gel is not freed when the ratio and concentration of silicate is below a specific level.

This phenomenon can be explained by the fact that when the ratio and concentration of silicate within water-glass decrease, the amount of opposing ions increases, the diffusion layer gets thicker and the stability of micelle becomes higher.

On the other hand, the higher the ratio and •concentration of silicate become, the lower the elasticity of 4 15 gel becomes, and gel with almost no elasticity can be obtained when the ratio of silicate is 3 or more.

ao S""Using water-glass with the silicate ratio at 3 or less is advantageous in regard to the fact that gel with broad activity can be obtained. However, as the silicate ratio increases, the amount of gel generated decreases and the 4 O.h consumption of additives used for denaturation increases.

Therefore, it is recommended to use water-glass with the silicate ratio between 2.4 The desirable amount of additives to be used for denaturation is between thirty (30) and forth (40) percent of the entire weight, which stabilizes the amount of gel generated.

The secondary denaturation of water-glass is a process wherein the elastic gel denatured primarily is dissolved into I i ii -1~ a 14 6 water-glass with the silicate ratio at 3 or more to obtain a vehicle with high silicate content, elasticity and adhesion.

In this case, it is recommended to adjust the weight ratio of PSE/SiO 2 to value between 0.1 and 100 or desirably between 1.0 and With the weight ratio below 0.1, the denaturing effect can not be expected. On the other hand, with the weight ratio at 100 or more, the stability of a strain and the physical characteristics of a film reduce.

The third denaturation is a denaturation process with aluminum compounds.

Denaturation with aluminum compounds is to quicken the film hardening and obtain a denatured vehicle that contains semizeolite structures.

In this case, it is recommended to adjust the mol ratio of AlgO 3 /SiO 2 to value between 0.05 and 0.2 or desirably between 0.08 and 0.12. With the mol ratio below 0.5, the Sdenaturing effect is lost. On the other hand, with the mol ratio at 0.2 or more, the stability of a strain and the work efficiency reduce.

The ion exchanged aluminosilicate that can be added to a vehicle as a permanent dispersing agent contributes to hasten the hardening and completion of a paint film and maintain the film's multifunctionability represented by anticorrosive and antifouling functions.

Aluminosilicate is ion exchanged partially or entirely by alkaline metals and rare metal ions.

This aluminosilicate has ion exchangeability and a strong electrostatic field and shows the characteristics of il 7 solid acid.

The aluminosilicate with solid acid and ion exchangeability acts with a denatured water-glass vehicle, performs such interactions as ion exchange, absorption, neutralization with free alkali, water, etc. and forms a waterproof, micropore structured zeolite paint film.

The film structure has been identified as of micropore structured zeolite by infrared absorption spectrum and X-ray diffraction analyses, surface analysis with ESCA, etc., differential thermal analysis and observation with a scanning electron microscope, etc.

The zeolite film not only reduces the oxygen density supplied to electrochemical positive reaction occurs on the iron surface by absorbing and retaining oxygen but also 15 provides anticorrosive and antifouling efficiencies with its Ssynthetical characteristics including ion exchange, oxygen absorption, electrostatic field, surface pH adjustment, etc.

The paint film has high coldproofness, shockproofness S and heatproofness. Water absorbed in the micropores does not freeze under ordinary conditions. It also has no more than 10 8 cm of resistivity as well as excellent electrification resistance, which enables itself to avoid the adhesion of dirt and generation of mold.

T As a result, this paint can stand to be used on ships, marine structures and submarine, sewage purification, and se.

water ion exchange and concentration facilities and other general facilities as paint that has excellent durability against salt, humidity, incombustible heat, corrosion, fouling, electrification, etc.

i -r i ~7~ 8 f 1 i Practical Example 1 Polyethylene glycol was added to a silicate solution whose mol ratio (SiO 2

/M

2 0: M includes Na, K, Li, NH 4 and NR 4 is 3.0 to obtain elastic gel with high silicate content (PSE).

This gel was then dissolved with silicate solution whose mol ratio (SiO 2

/M

2 0) is between 4.0 and 4.5 to turn the weight ratio of PSE/SiO 2 to be 1.0. And then aluminum sulfate was added to this mixture to turn the mol ratio of A1 2 0 3 /SiO 2 to be 0.08. After that, this mixture vas heated at 100 degrees of Celsius to obtain denatured silicate colloid solution.

Practical Example 2 The elastic gel obtained by the use of the same method as described in Practical Example 1 was dissolved with silicate solution whose mol ratio (SiO2/M20) is between and 4.5 to turn the weight ratio of PSE/SiO to be 1.0. And then aluminum sulfate was added to this mixture to turn the mol ratio of Al 2 0 3 /SiO 2 to be 0.16. After that, this mixture was heated at 100 degrees of Celsius to obtain denatured silicate colloid solution.

Practical Example 3 The elastic gel obtained by the use of the same method as described in Practical Example 1 was dissolved with silicate solution whose mol ratio (SiO 2

/M

2 0) is between and 4.5 to turn the weight ratio of PSE/SiO 2 to be 1.0. And then aluminum sulfate was added to this mixture to turn the mol ratio of Al 2 023/SiO 2 to be 0.24. After that, this mixture was heated at 100 degrees of Celsius to obtain F- 1V.

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.441 denatured silicate colloid solution.

Practical Example 4 Polyethylene glycol (n=3 or more) was added to silicate solution whose mol ratio SiO 2

/M

2 O: M includes Na, K, NH 4 and

HR

4 is between 2.4 and 2.6 to obtain elastic gel with high silicate content.

This high-siliceous elastic get was then dissolved with silicate solution whose mol ratio (SiO2/M 2 0) is between and 4.0 to turn the weight ratio of PSE/SiO 2 to be 10. And then aluminum sulfate was added to this mixture to turn the mol ratio of AlgO 3 /SiO 2 to be 0.24. After that, this mixture was heated at 100 degrees of Celsius to obtain denatured silicate colloid solution.

Practical Example 15 A paint with the following composition was mixed with a denatured silicate vehicle manufactured in the same way as described in Practical Example 1 and the mixture was applied to surface treated iron boards (90x50xmm and 300x300xmm) and left to dry for six days. An experiment was conducted after the boards had been soaked in a solution with 3 percent salt and sea water for one year.

Denatured silicate vehicle Mordenite ZnO 25 TiO 2 4wt% Iron titanate lwt% As a result of the experiment, no apparent change was observed on the boards; no adhesion of marine organisms was seen.

Practical Example 6 Paint with the following composition was added to a 04 14-

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0044 04 0 0 4 I L S 1 denatured silicate vehicle manufactured in the same 'way as described in Practical Example 2 and an experiment was conducted in the same way as described in Practical Example The paint was left to harden for four days.

Denatured silicate vehicle 42wt% Zeolite A 37wt% Clay ZnO 8wt% Iron titanate 3wt% As a result of the experiment, no apparent change was observed on the boards; no adhesion of marine organisms was seen.

Practical Example 7 Paint with the following composition was added to a denatured silicate vehicle manufactured in the same way as described in Practical Example 3 and an experiment was conducted in the same way as described in Practical Example The paint was left to harden for thz..e days.

Denatured silicate vehicle 40wt% i Mordenite 38wt% Clay TiO 2 3wt% ZnO MnO 2 2wt% 25 Fe0 3 2wt% 2 t SThe result of the experiment was exactly the same as those of Practical Examples 5 and 6.

Practical Example 8 C In Practical Examples 5, 6 and 7, the paint was applied to the body and bottom of a ship and a navigation test was conducted for eight years. However, no apparent change was ooserved on the boards; no adhesion of marine organisms was seen.

The material characteristics of the paint film in

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r ~i1 Practical Examples 5, 6 and 7 are as follows: Amount of paint applied 300-500 g/m 2 Thickness of paint applied 0.1-0.15 mm Bending strength 6-7 mm Shock strength 40-45 kg'cm Electrification resistance 108cm or less Surface strength (mos) 4-5 Heat resistance 600 C Salt tolerance more than 10 years in the ocean Practical Example 9 With a vehicle manufactured in the same way as described in Practical Example 8, exterior paint with the following composition was made and applied to cement and slate. A test was conducted for one year under natural conditions.

Denatured silicate vehicle Zeolite 5A Porcelain glaze BaSO 4 3wt% 20 White carbon 2wt% CaCO 3 3wt% Titanium white 2wt% r r i c

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The test results indicated no change on the paint film.

Practical Example With a vehicle manufactured in the same way as described in Practical Example 4, interior paint with the following composition was made and applied to a batch of cement and a piece of slate. Then they were retained for one year at twenty-five (25) degrees of Celsius and sixty (60) or more of relative humidity.

Denatured silicate vehicle Mordenite Porcelain glaze Titanium white White carbon 2wt% CaCO 3 3wt% The test results showed no generation of mold, dry peeling or adhesion of dirt.

(4 4 C a C (4 j .li Practical Example 11 With a vehicle manufactured in the same way described in Practical Example 4, inorganic paint with the following composition was made: Denatured silicate vehicle Zeolite Y BaSO 4 CaCO 3 3wt% Porcelain glaze 7wt% Pigment With this inorganic paint, pictures were painted on pieces of granite, cement materials, etc. and they were retained for one year at twenty-five (25) degrees of SCelsius and sixty (60) or more of relative humidity. As a 15 result, no change was observed.

The paints made in the ways described in Practical Example 8, 9, 10 and 11 showed the following characteristics after they hardened.

Amount of paint applied 400-500 g/m 2 Thickness of paint applied 0.1-0.2 mm Shock strength 40 45 kg cm Bending strength 6-7 mm Electrification resistance 10 8 ,'cm or less Heat resistance 1000 0

C

4 As explained above, with the invention, non-zinc, poisonless inorganic paint wherein poisonless antifouling and anticorrosive functions based on a denatured water-glass 4 vehicle and ion exchange aluminosilicate are concurrent and multifunctional inorganic paint which has strong adhesion to iron, ferro alloy, concrete, porcelain, wood, etc. and longterm waterproofness and excellent weatherproofness, incombustibility, heatproofness, electrification resistance, bactericidal action, etc. can be obtained. Moreover, paint that quickens the natural hardening speed as well as longers

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t i d 13 the work time prior to painting is made available.

The paint is micell-structured by ion exchanging, absorbing and neutralizing effects of aluminosilicate after being applied, becomes a siloxane polymer sequentially crosslinked and produces a strong paint film with hugh silicate molecules. Furthermore, the paint film has a special structure with micropores, an anticorrosive function, which consists of absorption and immobilization of oxide and inhibitation of iron, ion current, and a poisonless antifouling function, which ionizes amino acid calcium colloid of marine deposits. Therefore, the paint can be usefully applied to ships, marine structures and submarine, sewage purification, sea water ion exchange and concentration .9 cand other general facilities as paint that has excellent 9.o durability against salt, humidity, incombustible heat, corrosion, fouling, electrification, etc.

FIG 1 shows the amount of gel generated that changes according to the relative density of water-glass and the ratio of SiO 2

/M

2 0.

a. 9 2M r 4 I I B

Claims (8)

1. A method for manufacturing water-glass, non-zinc multifunctional paint by having a silicate M20nSiO 2 (M:K,Na, Li, n:2.0 3.0) solution reacted with low molecular, low polymerized organic compounds (alcohol, aldehyde ester and ether) which have functional groups to generate elastic gel with high silicate content (hereafter PSE), dissolving said PSE into a silicate M 2 0-nSiO 2 Na, Li, n:3.0 solution to turn the weight ratio of PSE/SiO 2 to be between 10 0.1 and 100, adding an aluminum compound to said solution to turn the weight ratio of Al 2 O 3 /SiO 2 to be between 0.05 and and heat and denature the mixture to obtain a silicate colloid vehicle and adding the aluminosilicate ion-exchanged with alkaline earth metals and transition metal ions and one or more than two types of fillers selected from alkaline earth metals and transition metal oxides to said vehicle to which a pigment is added.

2. The method for manufacturing a water-glass non-zinc multifunctional paint of claim 1 wherein a silicate solution whose mol ratio is within the range of 0.25 0.4 is reacted with low molecular weight, or polymerized organic compounds (polymerization degree n greater than 1 and up to 2000) to obtain an almost neutral denatured silicate elastic body whose pH is between 6.5 and

3. The method for manufacturing a water-glass non-zinc S multifunctional paint of claim 1 or 2 wherein an aluminum S Si1 ,ii i I I I (r ft I I t I ft f I I I I I It *fl ft I II Cr c LI *t L compound is added according to claim 2 to a solution whose weight ratio of PSE/SiO 2 is within the range of 1.0 10 to turn the mol ratio of A1 2 0 3 /SiO 2 to be between 0.9 and 5.0 to obtain a vehicle that contains a polysilicate elastic body 5 which has been heated at 100 degrees of Celsius to denature.

4. The method for manufacturing a water-glass non-zinc multifunctional paint of claim 1, 2 or 3 wherein a multifunctional paint that contains alkaline earth metals, rare earth metals, barium sulfate, zinc oxide, titanium oxide 10 and pigment is added to a denatured polysilicate elastic body vehicle.

The method for manufacturing a water-glass non-zinc multifunctional paint of claim 1, 2, 3 or 4 wherein a paint for ship's bottom use, in which a poisonless antifouling 15 effect which resolves an amino acid calcium colloid of an adhesive secrete ejected from an organism sticking to a ship concurrent with an anticorrosive effect, is obtained.

6. The method for manufacturing a water-glass non-zinc multifunctional paint of claim 1, 2, 3, 4 or 5 wherein a paint vehicle for decoration use, in which the weight ratio of PSE/SiO 2 is within the range of 0.1 100 and the mol ratio of A120 3 /SiO 2 is within the range of 1.0 5.0, is obtained.

7. The method for manufacturing a water-glass non-zinc multifunctional paint of claim 6, wherein the weight ratio of 16 PSE/SiO 2 is within the range of 1.0 -10 and the mol ratio of A1 2 0 3 /5i0 2 is within the range of 1.0

8. A water-glass non-zinc multifunctional paint prepared by a method as claimed in anyone of claims 1 7 that can be applied to iron, ferro alloy, wood, concrete, slate, glass, and cloth as a water-glass, non-zinc and liquid-type multifunctional paint. DATED this SIXTH day of JUNE 1995. KABUSHIKI KAISHA DAME KIKAI 410 By: THOMSON PIZZEY C C 1 1 ABSTRACT A method for manufacturing water-glass, non-zinc multifunctional paint by having a silicate M 2 0'nSiO 2 (M:K,Na, Li, n:2.0 3.0) solution reacted with low molecular, low polymerized organic compounds (alcohol, aldehyde ester and ether) which have functional groups to generate elastic gel with high silicate content (hereafter PSE), dissolving said PSE into a silicate M 2 O'nSiO 2 Na, Li, n:3.0 solution to turn the weight ratio of PSE/Si0 2 to be between 0.1 and 100, adding an aluminum compound to said solution to turn the weight ratio of Al 2 0/Si0 2 to be between 0.05 and u f i and heat and denature the mixture to obtain a silicate Scolloid vehicle and adding the aluminosilicate ion-exchanged with alkaline earth metals and transition metal ions and one or more than two types of fillers selected from alkaline earth metals and transition metal oxides to said vehicle to .r twhich a pigment is added. Li i 1 B