JPH0139710B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention is a semi-solid composition for water-stopping, and more specifically, it has the property that even if water or seawater enters the area where it is coated, applied, or filled, it will not be replaced by water or seawater. Relating to semi-solid compositions. The composition of the present invention is suitable for use as a water stopper, rust preventive agent, or lubricant when applied to metal structures that are exposed to rainwater or in contact with water, and is particularly suitable for use as a water stopper, rust preventive agent, or lubricant for metal structures that are exposed to rainwater or in contact with water.
Suitable for use as a rust-preventing lubricant and as a water-stopping and rust-preventing agent for tanker ballast tanks. (Prior technology) Roller bearings are often used for movable iron bearings for bridges, but the abutments and piers on which the bearings are installed are left open, making it difficult to prevent rainwater and dust from entering, and the bearings are extremely difficult to maintain. It is in an environment where it is easily corroded. The structure of a steel movable bearing of the roller bearing type for a bridge will be explained using Figure 1 for reference.
A steel roller 3 is inserted between the lower shoe 2 fixed to the bridge pier (not shown), and is structured to smoothly release expansion and contraction caused by temperature changes or deflection of the bridge superstructure. Usually, the roller 3 is placed in a tray 4 fixed to the lower shoe 2.
A hole 5 is bored in the bottom of the tray 4 for draining rainwater. Conventionally, in order to prevent corrosion of the bearings, especially the rollers 3 and the trays 4, oils, greases, solid lubricants, etc. have been applied and filled onto the rollers, the trays, and the like. In addition, oil tankers load ballast water into their tanks after discharging oil, but conventionally oil tankers are coated with grease to prevent corrosion of the tank's inner walls. (Problem to be solved by the invention) However, in the conventional method of using oil, grease, solid lubricant, etc. for maintenance of steel movable bearings of bridges, the applied and filled oil, grease, solid lubricant, etc. If rainwater leaks out of the holes, or if the holes are clogged or rainwater accumulates in the tray due to heavy rain, it will float on top of the water and overflow from the tray and flow away, so you must frequently apply oil or other oil to the roller. Moreover, since the movable bearings are located in locations that are difficult to access, maintenance and management of the movable bearings is very time-consuming. There is also the problem that oil and grease spilled from the saucer floats on the water surface and pollutes rivers and sea surfaces. In order to simplify the management of such steel movable bearings for bridges, it is necessary that once the material is applied to the parts of the movable bearing that require corrosion protection and lubrication, it will continue to function for a long period of time. Specifically, in order to be used satisfactorily for such purposes, it is considered desirable that the materials used have the following properties. In other words, since the application area is open, even if rainwater enters, it will not float on top of the rainwater or become emulsified, it will not flow through the hole at the bottom of the saucer, and the lubricant will not be supplied to the over-friction area. It has the function of repairing oil films, and the application area is open and exposed to wind and rain, so weather resistance is required.
It does not flow in the heat or bind in the cold, and since the movable bearing is made of iron, it has rust-proof properties, and has a certain load capacity.It is applied to bridge structures that are difficult to work on, so it is difficult to supply. Preferably something easy;
In the event that it falls into a river or sea, it must not float on the water surface and contaminate the sea or river. Further, in the conventional method of applying grease to the inner wall of the ballast tank of an oil tanker, there is a problem that the grease floats on the water surface when the ballast is discharged and pollutes the sea. (Means for Solving the Problems) The present inventors have solved the problems of the prior art, and have solved the problems of the prior art by using metal structures that are exposed to rainwater or in contact with water, such as bridge iron movable bearings and oil tanker ballast tanks. In order to protect these metal structures by applying it to water, a specific thixotropy imparting agent is added to a heavy base oil that is non-emulsifying, water-insoluble and has lubricating properties. Specifically, the specific gravity is heavier than water, and the viscosity decreases in areas where there is excessive rubbing, but the viscosity easily recovers in areas other than areas where there is excessive rubbing. However, the present invention was completed by discovering that it is sufficient to create a semi-solid water-stopping composition that has anti-sag properties, demulsifying properties, weather resistance, and anti-corrosion properties. That is, the gist of the present invention is that phosphoric acid esters,
Selected from the group consisting of chlorinated hydrocarbons, polyglycols, polyphenyl ethers, hindered esters, silicone oils, fluorinated hydrocarbons, phthalate esters, benzoic acid derivatives, and highly aromatic mineral oils. The base oil is one or more of the following and has a specific gravity (15/4°C) of 0.95 or more, and is blended with 0.5 to 30 wt% clay and 0.5 to 40 wt% fatty acid amide or wax. A semi-solid composition for water stopping is characterized by: The base oil that is the main component of the composition of the present invention includes phosphate esters such as triaryl phosphate such as tricresyl phosphate, trimethyl phosphate, trialkyl phosphate such as tributyl phosphate, and chlorinated paraffin. Chlorinated hydrocarbons such as polyoxypropylene glycol and polyoxybutylene glycol, polyphenyl ethers such as diphenyl ether, trimethylolpropane caprylic acid triester, trimethylolpropane oleate triester, etc. Hindered esters such as trimethylolpropane ester, pentaerythritol caprylic acid tetraester, and pentaerythritol oleate tetraester, silicone oils such as methylphenyl silicone and dimethyl silicone, chlorofluorocarbons, and chlorotrifluorocarbons. Fluorinated hydrocarbons such as fluoroethylene polymerized oil and tetrafluoroethylene polymerized oil, phthalate esters such as dimethyl phthalate and dibutyl phthalate, dialkylene glycol dibenzoates such as diethylene glycol dibenzoate and dipropylene glycol dibenzoate, etc. Consisting of one or more selected from the group consisting of benzoic acid derivatives and highly aromatic mineral oils, with a specific gravity (15/4°C) of approximately 0.95 or more, and if circumstances permit, a specific gravity (15/4°C) of approximately 1.0. The above are used.
It is preferable that the specific gravity is as heavy as possible, but it is difficult to obtain one with a specific gravity (15/4℃) exceeding about 1.5.
These compounds are non-emulsifying, water-insoluble, heavy lubricating oils with lubricating properties, and are blended as base oils in the composition of the present invention to make the composition of the present invention non-emulsifying, water-insoluble, and have a specific gravity. It makes it heavier and also gives it lubricity. Clay and fatty acid amide or wax are used together as a thickening agent that imparts thixotropic properties and heat-resistant anti-sagging properties to the composition of the present invention. Clay also adds weight to the final composition of the present invention. Examples of clays include montmorillonite, vermiculite, kaolinite, and halloysite, clay minerals that can form intercalation compounds and are used as thickening agents. Although the clay may be unmodified, it is preferably modified to make it lipophilic clay. For example, lipophilic clay is
42-8697, 42-19713, 43-14780, 47-
13422, 47-17143, 50-22565, 50-25108
As described in et. It is denatured. Regarding these modifiers, examples of aliphatic amines include those having at least 16 carbon atoms per molecule such as octadecylamine, didodecylamine, dioctadecylamine, tridodecylamine (aliphatic amines include, for example, oleinyl amines). Dimethyldioctadecylammonium iodine, dimethyldioctadecylammonium hydroxide, which may be an amine salt with an acid such as an acid, or may be obtained by reacting with an alkyl halide such as methyl iodide, or further reacting with an alkali such as potassium hydroxide. Examples of imidazolines include 2-heptadecenylimidazoline, 2-octadecylimidazoline, 2-dodecylimidazoline, and 4-octadecylimidazoline. , 1-β-hydroxyethyl-
Imidazolines having about 10 to 22 carbon atoms in one molecule and having a hydrocarbon group or further a hydroxyalkyl group or an amino group as a substituent, such as 2-heptadecyl imidazoline and 1-β-aminoethyl-2-heptadecyl imidazoline. Examples of aminoamides include diethylenetriamine,
A reaction product of a polyalkylene polyamine such as polyethylene polyamine with a molecular weight of about 220 to 450 and an aliphatic monocarboxylic acid having about 10 to 22 carbon atoms per molecule such as lauric acid, oleic acid, stearic acid, palmitic acid, etc. An example of an aminoplast resin is a co-condensate of the amines melamine and benzoguanamine, and an example of a polyepoxide resin is one obtained by curing polyepoxide with an organic amine curing agent. Clay can be added directly to the base oil and mixed to form a gel, but the clay can be mixed in advance with a polar solvent such as acetone, methyl ethyl ketone, methanol, ethanol, propanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, etc. It can be incorporated into the composition of the present invention by adding it to the base oil and mixing it to prepare a gel, and adding this gel to the base oil and stirring to gel the whole and heating to remove the polar solvent. preferable. In order to further enhance the effect of the clay mineral as an intercalation compound and to increase the intercalation effect of the intercalation compound, in addition to the use of the above-mentioned polar solvent, it is preferable to use a base oil having an aromatic ring such as highly aromatic mineral oil. Examples of fatty acid amides include stearic acid amide, oleic acid amide, ricinoleic acid amide, and N,N'-methylenebis fatty acid amide, which is a condensate of these fatty acid amides and formaldehyde. These fatty acid amides may have about 14 to 44 carbon atoms in one molecule. Examples of waxes include mineral waxes such as paraffin wax, carnauba wax, bead wax, and synthetic waxes, animal waxes, vegetable waxes, and synthetic waxes. The fatty acid amide and wax preferably have a specific gravity (15/4°C) of about 0.90 or more, preferably about 0.95 or more, and a melting point of about 100°C or more. Items with specific gravity (15/4℃) exceeding approximately 1.5,
It is difficult to obtain materials with a melting point above approximately 150℃. Those with a specific gravity (15/4°C) of less than about 0.90 may separate from heavy base oils, and those with a melting point of less than about 100°C may impart thixotropic and anti-sag properties to the composition when used in combination with clay. There is not enough ability to grant. Fatty acid amide and wax may be used alone or both. The combination of clay and fatty acid amide or wax imparts thixotropic and anti-sag properties to the composition. The preferred amount of clay is approximately 0.5~
30 wt%, especially about 1.0 to 10 wt% (based on the total composition), and the preferred total loading of fatty acid amide or wax is about 0.5 to 40 wt%, especially about 1.0 to 20 wt% (based on the total composition). If the amount of clay and fatty acid amide or wax blended is too small, the viscosity will not increase and the anti-sagging property will be low, and if the amount of these blended is too large, workability will deteriorate or the entire product will solidify. If necessary, antirust additives, antioxidants, lubricants (oil agents, load-bearing agents), etc., which are commonly used as lubricating oil additives, can be added to the composition of the present invention.
These additives may be added at the time of preparing the gel using the thickening agent, or may be added before or after the thickening agent. Examples of additives or compounding agents that impart rust prevention properties include rosins (colophoniums) such as abietic acid, carboxylic acid soaps such as lead naphthenate and aluminum stearate, sulfonic acid soaps such as calcium sulfonate, Nonionic surfactants such as polyoxyalkylene alkyl ethers, polyoxyalkylene alkyl phenol ethers, sorbitan fatty acid esters, polyoxyalkylene sorbitan fatty acid esters, and polyoxyalkylene esters are used. However, it should be noted here that the rust inhibitor used in the composition of the present invention is preferably one that does not dissolve in water even if it comes into contact with water and remains in the composition. In acid soaps, monovalent metal salts and amine salts are undesirable because they dissolve in water. Among nonionic surfactants, those with a high hydrophilic-lipophilic balance (HLB), for example, 4 or more, are highly soluble in water and are not preferred. The preferred amount of these antirust additives is approximately 0.1 to 15wt.
% (based on the total composition). Examples of antioxidants include bisphenols,
Naphthylamines, zinc dialkyldithiophosphates, ditertiarybutylalkylphenols, ketone-amine condensates, benzotriazoles, and the like are used. The preferred amount of antioxidant is about 0.1 to 10 wt% (based on the total composition). Examples of lubricants include tricresyl phosphate (which can also be used as a base oil), dibenzyl disulfide, sulfur-treated olefins, and oleic acid. The preferred amount of lubricant is approximately 0.1~
30wt% (based on the entire composition). In order to provide the composition of the present invention with waterproof properties, the specific gravity of the composition needs to be heavier than water or seawater. Specifically, by selecting the above base oil, thickener, and additives, the final composition has a specific gravity (15/4°C) of approximately 1.02.
In particular, it is preferably about 1.04 or more. The higher the specific gravity of the composition, the better, but it is difficult to obtain a composition with a specific gravity (15/4°C) of more than about 1.7 due to the availability of base oil and additives. The use of the base oils described above also renders the final composition water-insoluble and non-emulsifying. (Effects of the Invention) The semi-solid composition of the present invention exhibits thixotropic properties and has excellent anti-sag properties, has a water-stop property (not replaced by water) because its specific gravity is heavier than water, is water-insoluble and has demulsifying properties, Excellent weather resistance. Furthermore, since synthetic lubricating oil is used as the base oil, it also has load resistance and rust prevention properties (these can be further improved by using additives). Therefore, the composition of the present invention is useful as a semi-solid composition for waterproofing, which is applied to or filled into metal structures that are exposed to rainwater, wind dust, or in contact with water to protect the metal structures.
Specific examples include water-stopping of movable steel bearings for bridges,
It can be used as a rust-preventing lubricant, or as a water-stopping and rust-preventing agent for the inner walls of oil tanker ballast tanks. Since the composition of the present invention is semi-solid, it is easy to supply the composition even if these metal structures are difficult to work with. Furthermore, since the composition of the present invention is heavier than water, even if it falls into a river or the sea during use, it does not float on the water surface but sinks to the riverbed or seabed, so it has the advantage of causing fewer problems in terms of pollution. (Example) Next, the present invention will be further explained with reference to Examples. Examples 1 to 5 Waterstop semisolid compositions A, B, C, D, E according to the invention from base oil, thickener and other additives
(referred to as Examples 1, 2, 3, 4, and 5, respectively) were prepared. Its composition is as follows. Composition A (Example 1) Base oil: Dimethyl phthalate 45.0wt% Polyoxypropylene glycol (molecular weight 2000) 25.0 Aromatic mineral oil (specific gravity 15/4°C, 0.98)
10.0wt% Thickener: Montmorillonite 4.0 〃 N,N-methylenebisstearamide 8.0 〃 Additive: Rosin 7.0 〃 Tetraoxyethylene glycol tributyl phenol ether 1.0 〃 (Note) Montmorillonite absorbs dimethyldioctadecylammonium hydroxide. It is a lipophilic montmorillonite modified with a grain size of 0.5μ or less and a true specific gravity of 1.70. Example 2~
The same one used for 5. Composition B (Example 2) Base oil: Dimethyl phthalate 45.0wt% Polyoxypropylene glycol (molecular weight 2000) 25.0 Aromatic mineral oil (specific gravity 15/4°C 0.98)
10.0 〃 Thickening agent: Montmorillonite 5.0 〃 Stearamide 4.0 〃 Additive: Rosin 10.0 〃 Tetraoxyethylene glycol tributyl phenol ether 1.0wt% Composition C (Example 3) Base oil: Diethylene glycol dibenzoate
50.0wt% aromatic mineral oil (specific gravity 15/4℃, 0.98)
24.0 Thickener: Montmorillonite 5.0 Carnauba wax 10.0 Additive: Rosin 5.0 Calcium sulfonate (molecular weight 1000) 6.0 Composition D (Example 4) Base oil: Dimethylfucrate 40.0wt% Trimethylolpropane caprylate Ester 36.0 〃 Tricresyl phosphate 10.0 〃 Thickening agent: Montmorillonite 4.0 〃 N,N'-methylene bisstearamide 4.0 〃 Additive: Calcium sulfonate (molecular weight 1000) 5.0 〃 4,4'-Butylidene bis(6-tercia) butyl-3-methylphenol)
1.0wt% Composition E (Example 5) Base oil: dimethyl phthalate 23.0wt% Pentaerythritol oleate tetraester 30.0 Diphenyl ether 25.0 Thickening agent: Montmorillonite 5.0 Polyethylene wax (molecular weight 3000,
Melting point: 120℃) 10.0 〃 Additive: Rosin 5.0 〃 Tetraoxyethylene glycol tributyl phenol ether 1.0 〃 Trimethyldihydroquinoline
1.0 Evaluation tests for compositions A to E of Examples 1 to 5 were conducted using the methods described in the following table.

【table】

【table】

[Table] The evaluation test results of compositions A to E of Examples 1 to 5 are shown in the following table.

[Table] As can be seen from Table 2, compositions A to E of Examples 1 to 5 were semisolids with specific gravity heavier than water and had water-stop properties. It also has thixotropic properties that return to its original semi-solid state after viscosity measurement, and has excellent anti-sag properties. It can be seen that these compositions have good weather resistance because they have excellent low temperature resistance and anti-sagging properties. In addition, these compositions have excellent water resistance, demulsifying properties, oxidation stability, and rust prevention properties, and since the base oil, which is the main component, is a synthetic lubricating oil, they have good lubricity. Since it sinks to the ocean floor, there are few pollution problems. The desired properties for a water-stopping and rust-preventing lubricant suitable for use in the maintenance of movable bridge steel bearings are a specific gravity (15/4°C) of approximately 1.02 or higher and a viscosity of approximately 100,000 to 500,000.
CP/40℃, approx. 50,000 to 250,000CP/60℃, anti-sagging properties, not falling below the marked line, low temperature resistance, water resistance,
Compositions A to E of Examples 1 to 5 were tested because they all passed the demulsifying property, no rust occurred for about 1000 hours or more in a wet test, and had lubricity.
All of these are suitable as water-stopping and rust-preventing lubricants for bridge iron movable bearings. Moreover, since those having such characteristics can be suitably used as a water-stopping and rust preventive agent for the inner wall of an oil tanker's ballast tank, the compositions of Examples 1 to 5 can also be used as a water-stopping and rust-preventing agent for the inner wall of an oil tanker's ballast tank. It can also be suitably used as a rust preventive agent. (Comparative Example) Next, an example of a case where the present invention is not satisfied will be explained using a comparative example. Comparative Examples 1 and 2 Composition F containing only clay as a thickening agent and containing no fatty acid amide or wax (referred to as Comparative Example 1); and Composition F containing only fatty acid amide as a thickening agent and containing no clay. Product G (Comparative Example 2
shall be. ) was prepared. Its composition is as follows. Composition F (Comparative Example 1) Base oil: Dimethyl phthalate 45.0wt% Polyoxypropylene glycol (molecular weight 2000) 25.0wt% Aromatic mineral oil (specific gravity 15/4°C, 0.98)
14.0wt% Thickener: Montmorillonite 8.0wt% Additive: Rosin 7.0wt% Tetraoxyethylene glycol tributyl phenol ether 1.0wt% (Note) Montmorillonite is made of lipophilic montmorillonite modified by absorbing dimethyldioctadecylammonium hydroxide. It has a diameter of 0.5μ or less and a true specific gravity of 1.70. Composition G (Comparative Example 2) Base oil: dimethyl phthalate 45.0wt% polyoxypropylene glycol
25.0wt% (molecular weight 2000) Aromatic mineral oil (specific gravity 15/4℃, 0.98)
10.0wt% Thickener: N,N'-methylenebisstearamide 12.0wt% Additive: Rosin 7.0wt% Tetraoxyethylene glycol tributyl phenol ether 1.0wt% Evaluation of compositions F and G of Comparative Examples 1 and 2 The test was conducted in the same manner as in the examples. The results are shown in the table below.

【table】

[Table] As can be seen from Table 3, compositions F and G of Comparative Examples 1 and 2 have a specific gravity higher than water, but do not satisfy anti-sagging properties and low temperature resistance, and have problems in weather resistance. It also has thixotropy, which returns to its original semi-solid state after viscosity measurement, but this is not sufficient. In particular, Composition F of Comparative Example 1, which contains only clay as a thickening agent and does not contain fatty acid amide or wax, is also unsatisfactory in water resistance, pore emulsification properties, and rust prevention properties. Than these things,
It can be seen that it is necessary to use clay and a fatty acid amide or wax together as a thickening agent to impart thixotropic properties and heat-resistant anti-sagging properties to the composition of the present invention.

[Brief explanation of drawings]

FIG. 1 is a partially transparent front view of a bridge iron movable bearing, which is an example of an article to which the composition of the present invention is applied. 1...Upper shoe, 2...Lower shoe, 3...Roller,
4...Saucer, 5...Drain hole.

Claims (1)

[Claims] 1 Phosphate esters, chlorinated hydrocarbons, polyglycols, polyphenyl ethers, hindered esters, silicone oils, fluorinated hydrocarbons, phthalate esters, benzoic acid derivatives, and highly aromatic Contains one or more types selected from the group consisting of mineral oils and has a specific gravity (15/4℃)
Use 0.95 or higher as a base oil, and add 0.5 to 30wt% to this
A semi-solid composition for water-stopping, characterized in that it is a mixture of clay and 0.5 to 40 wt% of fatty acid amide or wax.