JPS612763A - Anticorrosive rubber coating material - Google Patents

Abstract

PURPOSE:The titled rubber coating material, obtained by forming a solution of a rubber component containing butyl rubber, chlorosulfonate polyethylene and/or chlorinated rubber in a specific proportion, capable of exhibiting anticorrosive function for a long period, and capable of thick coating only by one kind of one- pack type coating material. CONSTITUTION:An anticorrosive coating material obtained by dissolving a rubber component consisting of (A) preferably reclamined butyl rubber and butyl rubber containing 10-70wt%, based on the total rubber component, butyl rubber, (B) chlorosulfonated polyethylene and/or (C) chlorinated rubber in a solvent, e.g. toluene. EFFECT:Improved environment interception performance, e.g. acids, particularly organic acids, salt water alkalis, etc., adhesion after heat cycles, rubber elasticity represented by impact resistance, storage stability and recoating adhesion. USE:Inner surface of sewage drain pipes and sewage treatment-related facilitates, vehicles, ships and bridges, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an anticorrosion rubber coating, and more particularly to an anticorrosion rubber coating prepared by dissolving a rubber component consisting of butyl rubber, chlorosulfonated polyethylene, and/or chlorinated rubber.

Rust prevention measures have been taken on iron surfaces for a long time, and there are a wide variety of methods, but one method that is superior in terms of performance and workability is to coat the iron surface with paint and isolate it from an environment that is prone to rusting. There are known ways to do this. However, in areas where heavy corrosion protection is required, such as in adverse environments, such as sewage-related facilities and the inside surfaces of drainage pipes, factory facilities, marine structures, ships, and bridges, it is necessary to apply several coats of paint several times or several types of paint. However, in spite of this, the anticorrosion performance and durability are not sufficient, and there is a desire for a paint that has long-term anticorrosion performance.

That is, the drawback of conventional paints is (1) Coating J#+ All constituent polymer components have low molecular weights, so chemical stability including chemical resistance is not sufficient. ■Because the rubber outsourcing of the paint is poor and it lacks flexibility, the stress experienced between the coated object and the paint and between different types of paint due to seasonal temperature changes increases, resulting in a lack of long-term close contact with the trap. ■Poor performance in blocking oxidation-promoting substances including gases. ■Apply several types of paint! There are many types that require mixing for two nights, making it easy to make work errors and cause variations in coating film performance. Therefore, the present inventors have conducted extensive research aimed at solving these shortcomings, exhibiting long-term anticorrosion performance, and being able to apply thick coatings with only one liquid injection of one type of paint, and have developed the present invention. I was able to complete it.

The feature of the present invention is that the vehicle is a rubber component that combines the environmental barrier performance of butyl rubber with the weather resistance, high hardness, and beautiful finish of the coating film of chlorosulfonated polyethylene and /X1 chlorinated rubber.

To explain in detail, until the present inventors recently proposed all butyl rubber paints, rubber paints were limited to chlorinated rubber, chlorinated rubber, and chlorosulfonated polyethylene. Rubber paints have a low molecular weight and have shortcomings in impact resistance and adhesion between coats, while chlorsulfonated polyethylene paints have excellent weather resistance but cannot achieve the goal of corrosion resistance.

In addition, the reason why rubber paints have not developed in the past is that Rubber L generally has a high molecular weight, so it is difficult to dissolve, and the commonly understood ones have low viscosity and lack paint workability and storage stability. There is. ■The coating film of rubber is too soft, and there is no suitable room-temperature crosslinking method to solve this problem. can be mentioned.

The inventors of the present invention were able to solve the above two problems by the following method after repeated trial and error in trying to eliminate 'kM.

That is, to solve the problem (2), by kneading the rubber component with a general-purpose rubber mixing machine such as an open roll or kneader and adjusting the Mooney viscosity of the rubber component, it becomes easier to dissolve.
Furthermore, the viscosity after dissolution and paintability were also improved. Father, viscosity stability after dissolution.

It was also confirmed that coating properties were significantly improved by changing the solvent composition.

Next, regarding the problem (2), by using Kuroshif 1-fluorinated polyethylene and/or chlorinated rubber, it was possible to obtain a coating film with optical hardness without crosslinking.

Therefore, the present inventors focused on butyl rubber, which has excellent environmental barrier performance, and proposed a butyl rubber paint.This butyl rubber paint also has results that far exceed conventional anticorrosive paints in terms of anticorrosion performance. However, there was a drawback that the coating film was easily scratched due to its low coating hardness. Therefore, we have proposed a type that uses epoxy resin and a type that uses cement, but the above type also uses epoxy resin.
It has drawbacks such as the difficulty in heating the two liquids and the risk of making errors in measuring and mixing during work, and in the case of a cement-based method, the coating film is brittle. Therefore, the present inventors maintained the excellent anti-corrosion effect of butyl rubber paint,
Furthermore, in order to eliminate the drawbacks of the countermeasure products mentioned above, various polymer kumquats were used through trial and error. As a result, a rubber paint consisting of a rubber component that combines butyl rubber with chlorosulfonated polyethylene and/or chlorinated rubber exhibits long-term corrosion protection with only one type of one-liquid paint, and can overcome the lack of hardness of butyl rubber paint. It was confirmed that the problem could be solved, and the present invention was completed.

That is, the anticorrosive rubber paint of the present invention is mainly composed of a desired solvent and a rubber component dissolved and dispersed in the solvent, wherein the rubber component is butyl rubber, chlorosulfonated polyethylene, and/or chlorinated rubber, and the butyl rubber accounts for 10 to 70% of the total rubber component. Further, in the present invention, the above-mentioned butyl rubber can be made into recycled butyl rubber.

Next, the constituent components of the present invention will be described.

In the present invention, the rubber component includes butyl rubber, chlorosulfonated polyethylene, and/or chlorinated rubber. Furthermore, butyl rubber (g) refers to virgin phthyl rubber, recycled butyl rubber, chlorinated phtyl rubber, brominated butyl rubber, partially crosslinked butyl rubber, and polyisobutylene.Butyl rubber, as is well known, has one of the best gas barrier properties among polymers including rubber. It can be said that rubber is indispensable for tire tubes and other parts that require gas barrier properties.

This is because paint containing butyl rubber is exposed to corrosive gases such as oxygen, chlorine, and sulfur dioxide.
l! This shows that it has a great effect in preventing [ from penetrating into the corrosion-protected member.

In addition, among butyl rubbers, recycled butyl rubber in particular is made by pulverizing butyl rubber that has been sulfurized as is known, so recycled rubber is naturally chemically stable because it has fewer bezel bonding parts than vernon butyl rubber. It has characteristics such as improved heat resistance due to the presence of O-sulfur gel content, and completely eliminates the flow phenomenon that occurs when left at low temperatures for long periods of time, which is often a problem with virgin butyl rubber. It offers unparalleled performance. As mentioned above, other butyl rubbers include chlorinated butyl rubber including virgin butyl rubber, brominated methyl rubber, partially cross-linked butyl rubber, and polyisobutyl rubber, but these butyl rubbers including recycled butyl rubber have a high dissolution efficiency, coating performance, It is preferable to use them alone or in combination in consideration of painting workability, storage stability, etc. The proportion of butyl rubber in the rubber component is preferably 10 to 70% by weight, more preferably 15 to 50% by weight. When the proportion of butyl rubber in the rubber component is less than 10% by weight, the environmental barrier performance is poor, and the organic acid resistance and adhesion are also poor. On the contrary, 70X'
When it exceeds t%, the coating film hardness is low and the coating film is easily scratched.

Next, talking about Tarolsul 7-ionized polyethylene, Tarolsulfonated polyethylene has no double bonds and is a polymer with excellent chemical stability, and is known to have particularly excellent weather resistance. The disadvantage is that it is inferior to custom-made products. However, this drawback can be improved by combining it with the above-mentioned butyl rubber and/or chlorinated rubber.

Tarolsul 7-ionized polyethylene is a polymer with excellent weather resistance, and it is desirable to increase its proportion in the rubber component for applications that particularly require weather resistance, but if used in large quantities, corrosion resistance and This is not preferred because the chalking notes are inferior. On the other hand, if the amount is small, the impact resistance, bending resistance, and appearance of the coating film will be poor.

Next, talking about chlorinated rubber, what is chlorinated rubber (06H
7C13)X<05H6CI4)yCC1oH1lC1
4) The chemical structure represented by z consists of p,
Although it is used as an anti-corrosion rubber paint, rubber paint made of chlorinated rubber alone has a low molecular weight and has disadvantages as a rubber paint in terms of adhesiveness after heat cycling, impact coating, and heat cycle. Although the anticorrosion performance for edible use is not satisfactory, it greatly improves the low hardness and scratchiness of butyl rubber paints, which are disadvantages of butyl rubber paints. If the proportion of chlorinated rubber in the rubber component is small, the hardness will be low, it will lag easily, and the adhesion will be poor; on the other hand, if the proportion is large! IIT impact 1 life, bending resistance inferior to dense N injection after heat cycle.

The structure of the present invention uses the above-mentioned rubber component as a vehicle, a solvent,
It consists of fillers, additives, etc., which will be described in order below.

TG agents and n Aromatic hydrocarbons such as toluene, xylene, and aromatic petroleum naphtha, aliphatic hydrocarbons such as hexane, ketones such as methyl ethyl ketone and methyl isobutyl ketone, esters such as methyl acetate and butyl acetate, and methanol. , alcohols such as ethanol and isoflobil alcohol, ethylene glycol, and ethylene glycol derivatives such as monomethyl ether ethylene glycol monoethyl ether acetate, etc., and may be used alone or in an appropriate combination of two or more. Viscosity as known to solvents.

Effect A on paint film drying, painting work, viscosity stability, etc.
Both are important, and it is desirable to use a combination of a V good solvent and a poor solvent depending on the composition of the rubber component.

Fillers include coloring pigments such as iron oxide, zinc oxide, titanium oxide, and carbon, anti-bulk pigments such as red lead, yellow lead, and zinc dust, calcium carbonate, talc, clay, fine powder adhesive, barium sulfate, mica, and ferrite. , glass flakes, etc.
Can be used alone or in combination of two or more types. These are paint film physical properties and corrosion protection notes.

This affects economic efficiency, etc.

Additives include thickeners, leveling agents, antifoaming agents, antifouling agents, anti-foaming agents, antibacterial agents, insect repellents, antioxidants, ultraviolet absorbers,
They are coupling agents, surfactant agents, etc., and may be used alone or in combination of two or more.

In addition, resins such as phenol resins, epoxy resins, terpene resins, and oil-based resins, softeners, and plasticizers may be added to improve various workability and to modify coating films.

Next, an example of the method for manufacturing the anticorrosive rubber paint of the present invention will be described, but the present invention is not limited to the following example of the manufacturing method.

First, the rubber component is kneaded using a pressure kneader, the Mooney viscosity is adjusted, the mixture is cut into small pieces, stirred and dissolved in some solvent, the filler is added, and then the necessary additives are added as needed, and the mixture is stirred and dispersed. After that, the remaining solvent is passed through an ink roll and stirred until it is sufficiently uniform to form a paint.

Next, the entire method of using the anticorrosive rubber paint of the present invention will be explained.

The anti-corrosion rubber paint of the present invention can be produced using the same method as for ordinary paints.
Sokuchi, airless spray, air spray, brush painting,
It can be applied by roller brush application, etc., and may be applied by any method.

Next, the present invention will be further explained with reference to Examples and Comparative Examples VC. Test method and determination method 1. Preparation of Samples All samples except for moisture permeability and storage stability were prepared using 5S-41 steel plates (approximately 200 x 100 x 4 m) with a dry coating thickness of 350 μm. Moisture permeability is dry coating thickness 100%
μ, a film-like coating was prepared and used as a sample.

2. Chemical resistance test: 10% each of acetic acid, butyric acid, lactic acid, sulfuric acid, and sodium hydroxide.
% aqueous solution and immersed at room temperature for 6 months, the paint film showed rust, blistering, and one crack in peeling.

Items with no abnormalities such as swelling or coloring of the chemical solution were evaluated as ○, and items with abnormalities were evaluated as ×.08 Shock resistance according to JIS-54006, Section 13 A method After conducting the test, follow JIS-54007, Section 8!
After 1,000 hours of salt water spraying, the area that received the impact was coated with a diameter of 20al1 or more centered around the point where the weight fell, with no abnormalities such as rust, blistering, peeling or cracking, and the coating on other parts remained intact. If the film does not show any abnormalities such as rust, blistering, peeling, cracking, etc., mark it as ○, and in other cases, mark as ×.
And so.

4 Weather Resistance After 6 months of outdoor exposure, the appearance of the paint film was checked for abnormal sounds, and those that were not acceptable were marked ○, and those with abnormalities were marked ×.

5 Scratch marks reaching the base material were carved with a single-edged razor on the coast-resistant bonding sample, and the coating was repeatedly dried twice a day and immersed in seawater using the ebb and flow of seawater. I checked to see if it was there. Within a width of 3 mm on each side along the scratch mark and a total of 6 mm [rust.

Items with abnormalities such as blistering and peeling are ○, dust on one side along the scratch mark trap 311 + total 6 #11 width or more, rust, bulges on one side within a width of 5 + total 10 mm,
Cases in which abnormalities such as peeling were observed were marked as △0, and cases in which the abnormality spread over a total of 10 fights in 5 sections on one side were marked as ×.

6 Moisture permeability According to JIS-Z-0208K, measured with approximately 10.0μ (7) film-like coating, moisture permeability is 0.5f/II]2.
The case of 24 hours or less was 0.0.517/m2, and the case of 24 hours or more was rated x.

7. Adhesion after heat cycle After preparing the sample and curing at room temperature for 7 days, cut a cutting edge that reaches the substrate so that the adhesive area is 1 inch square, and use a tensile tester to test the coating film vertically at 200 x j + /min. After measuring all the adhesive strength in the normal state, it was pulled at 80℃
One cycle is a heat cycle of 16 hours at 10'o and 10'o, and after repeating 30 cycles, the same adhesion test as in the normal state is conducted. Those below yo% were marked as x.

8. Prepare a sample using the method of 1. After it becomes tack-free, expose it to the outdoors for 2 hours, and apply the paint again in the same manner as in 1. A term with a measurement score of 8 or more is marked as ○, and a term with a score of 8 or less is marked as ×.

9. Impact resistance According to JIS-54006, Paragraph 13 A method, the area around the point where the weight falls is removed, and the diameter of the part that is easily separated from the base is O within 2Qj11 centered on the point of fall, and 20111
1 or more was marked as x.

10 Storage stable paint Measure the viscosity one day after tabulation and the viscosity after six months, and if the rate of change is within ±lθ% and there is no phase separation or sedimentation, mark it as ○, otherwise The case was marked as ×.

11 Paint film appearance Observe with the naked eye, see bulges, cracks, holes, and bulges.

Smoothness, coating film unevenness, etc. were checked, and the case where no abnormality was observed was rated ○, and the case where abnormality was observed was rated ×.

Example 1.2 is an anti-corrosion rubber paint of the present invention, which has excellent chemical resistance, salt spray resistance, weather resistance, coastal exposure resistance, adhesion after cycling, and rubber elasticity as represented by 51 resistance. Excellent,
In addition, it has excellent storage stability and adhesion upon repeated coating.

Comparative Example 1 shows a case where the butyl rubber content is less than 10% by weight in the rubber component, and it is understood that the environmental barrier properties are poor.

In Comparative Example 2, all cases where the butyl rubber content in the rubber component was 70% or more by weight were found to be poor in storage stability and coating appearance.

Comparative Example 3 shows a case in which butyl rubber is 10% by weight or less in the rubber component, and a case in which chlorosulfonated polyethylene occupies most of the rubber component.

It can be seen that this is superior to rubber bullet 11, but inferior in environmental isolation.

Ratio Example 4 shows a case where butyl rubber is 10% by weight or less in the rubber component, and a case where chlorinated rubber occupies most of the rubber component. It can be seen that this is inferior in rubber elasticity, recoating adhesion, and organic acid resistance.

Comparative Example 5 shows a combination of a commercially available zinc rich brimer and a commercially available tar epoxy, and it can be seen that the can adhesion, impact resistance, and coating adhesion after heat cycling are inferior.

Comparative Example 6 shows a case in which a commercially available zinc-rich primer, a commercially available epoxy paint, and a commercially available urethane paint are combined,
It can be seen that the salt spray resistance and coating vII adhesion after impact resistance are inferior.

As mentioned above, the anticorrosive rubber paint of the present invention has excellent environmental barrier performance against organic and inorganic acids, salt water, alkalis, etc., and in particular, its resistance to organic acids is far superior to paints currently used for heavy corrosion protection applications. The difference? It is effective for applications that are easily affected by organic acids, such as the inner surface of sewage drainage pipes and sewage treatment-related facilities.

It also exhibits excellent impact resistance and bending resistance,
In particular, the corrosion resistance after impact is significantly different from that of paints currently used for heavy-duty corrosion protection applications.Even if the surface of the object to be coated is damaged to the extent that it is exposed, the speed of propagation to the surrounding area will be reduced. - The anticorrosive rubber paint of the present invention forms a coating film with rubber elasticity, can follow the distortion of the coated object even when subjected to impact, and maintains adhesion and environmental barrier properties. It shows. Furthermore, the anticorrosive rubber paint of the present invention has excellent recoatability, and even if the surface of the object to be coated is exposed, it can be easily repaired, and problems such as delamination in the repaired area do not occur. From this point on, vehicles, ships.

This shows that it can provide long-term corrosion protection for applications that are easily affected by impacts, such as offshore structures.

Next, it has excellent adhesion after heat cycle,
It shows that it has high resistance to distortion caused by the difference in linear expansion coefficient between the coated object and the paint due to seasonal temperature changes, and temperature change Kondo is suitable for easy applications and constant vibration. Therefore, this shows that it is effective for applications where distortion is easily experienced between the object to be coated and the paint and between the paints, such as bridges, large structures, ships, vehicles, etc.

Father, the anticorrosive rubber paint of the present invention does not require the use of other materials such as primers, is liquid-based, allows for a very long recoating time, and has good recoat adhesion, so it is available in several types. There is no need to take into account the allowable time for recoating the paint, and to organize the entire process, eliminating work errors associated with mixing two components, and making it possible to efficiently form a stable paint film on the surface of the object to be coated. , there is also the advantage of shortening the process.

Furthermore, when the anticorrosive rubber paint of the present invention contains recycled butyl rubber, it is not long enough to improve chemical stability and heat resistance in terms of performance, and since the recycled butyl rubber is recycled from tire tubes, There is also the added benefit of effective use of resources.

As mentioned above, the anti-corrosion rubber paint of the present invention has a level of improvement that cannot be found in conventional anti-corrosion paints! ! It is an anti-corrosion paint that forms a rubber elastic coating that can exhibit long-term anti-corrosion performance using only one-component paint of the same type. It contributes to extending the life cycle in the field of

Procedural amendment dated July 25, 1980■, Small case indication 1982 Patent Application No. 122100 2, Title of invention: Anticorrosion rubber paint 3, Relationship with the case filed by amendment Patent applicant: Hayakawa Rubber Co., Ltd. Company 5゜6, Subject of amendment Column 7 of Detailed Description of the Invention J of the specification, Contents of amendment (as attached) 1. 1 Chlorthuri7ionization 1 on page 4, line 14 of the specification.
Corrected to ``Chlorsulfonation.''

2. On page 15, line 16 of the same page, ``electrification adhesion'' is corrected to ``overcoat adhesion,'' and on page 18, ``2 hours'' is corrected to ``2 weeks.''

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Claims (1)

[Scope of Claims] 1. An anticorrosive rubber coating mainly consisting of a desired solvent and a rubber component dissolved and dispersed therein, wherein the rubber component is composed of butyl rubber, chlorosulfonated polyethylene, and/or chlorinated rubber. and the butyl rubber accounts for 10 to 7 of the total rubber components.
An anticorrosive rubber paint characterized by having a content of 0% by weight. 2. The anticorrosive rubber paint according to claim 1, wherein the butyl rubber is recycled butyl rubber.