JPS61241379A - Water-stopping semi-solid composition - Google Patents

Abstract

PURPOSE:To provide the titled composition exhibiting thixotropic property, having high sag resistance, higher specific gravity than water and water-stopping property, insoluble in water and useful for the water-stopping of a movable iron support of bridge, by compounding clay and a fatty acid amide or a wax to a specific base oil. CONSTITUTION:The objective composition can be produced by compounding (A) a base oil having a specific gravity (15/4 deg.C) of >=0.95 and composed of one or more components selected from phosphate, chlorinated hydrocarbon, polyglycol, polyphenyl ether, hindered ester, silicone oil, fluorinated hydrocarbon, pathalate, benzoic acid derivative and a high-aromatic mineral oil with (B) a clay (e.g. monmorillonite) and (C) a fatty acid amide or a wax.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a semi-solid composition for waterproofing, and more specifically, the present invention provides a semi-solid composition for waterproofing. The present invention relates to a semi-solid composition that has the property of not being replaced by seawater. The composition of the present invention is suitable for use as a water stopper, rust preventive agent, or lubricant when applied to metal structures exposed to rainwater or in contact with water. Suitable for use as a dual-purpose lubricant and as a water-stopping and rust-inhibiting agent for tanker ballast tanks.

(Conventional technology) Roller bearings are often used as movable iron bearings for bridges, and the abutments on which the bearings are installed.

The piers remain open to prevent rainwater and dust from entering.
Bearings are in a highly corrosive environment. The structure of a steel movable bearing of the roller bearing type for a bridge will be explained with reference to Fig. 1 for reference.The upper shoe 1 is fixed to the upper structure of the bridge (not shown), and the bridge pier (not shown) is fixed to K. A steel roller 3 is inserted between the lower shoe 2 and is structured to smoothly expand and contract due to temperature changes or deflections of the bridge superstructure. Ordinary.

The roller 3 is fixed to the lower shoe 2, and the receiver is placed in a tray 4, and the tray 4 has a hole 5 at the bottom for draining rainwater. Conventionally, in order to prevent corrosion of the plate 4 of the roller 3 and the receiver, oil, grease, solid lubricant, etc. have been applied and filled onto the roller, the receiver, and the plate.

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 oil, grease, solid lubricant, etc. If rain water collects in the blood of the receiver due to heavy rainfall, it will float on top of the water and the receiver will overflow from the plate and flow away. Maintenance and management of movable bearings is very time-consuming because the movable bearings have to be coated and the movable bearings are located in locations that are difficult to access. Another problem with the receiver is that oil and grease spilled from the tray floats on the water surface, contaminating rivers and sea surfaces.

In order to simplify the management of such iron 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 maintain its effect for a long period of time. Specifically, in order to be able to satisfactorily use K for such purposes, it is considered desirable that the K used have the following properties. In other words, ■The applied area is open, so even if rainwater enters, it will not float on top of the rainwater and be washed away, or emulsified soot will not flow away.■The catch will not flow through the hole at the bottom of the dish and will not be damaged by friction. It has the function of supplying oil and repairing oil film, ■ The application area is open and exposed to wind and rain, so weather resistance is required, so it does not run away in the heat or freeze in the cold.■ The spinnable bearing is Since it is made of iron, it has anti-rust properties.
In addition, it has a certain load capacity, and ■Since the application site is a bridge structure that is difficult to work on, it is preferable that it be easily supplied.
■It must not float on the water surface and contaminate the sea or river if it falls into a river or sea.

In the conventional method, grease is applied to the inner wall of the palast tank of Mata oil tankers.

Grease has the problem of floating on the water surface when ballast is discharged and polluting 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, it is non-emulsifying and water-insoluble.

All you need to do is blend a specific cynothrobizing agent into a heavy base oil that has lubricating properties and make it rocky so that it has water-stopping properties, that is, the property that it is difficult to be replaced even when water enters. It is heavy and has xyxotropic properties that reduce the viscosity in areas where there is a lot of friction and recovers it easily in areas other than the areas where there is a lot of friction. It also has anti-sag properties, and is also water-stopping with demulsifying properties, weather resistance, and rust prevention properties. The present invention was completed by discovering that it can be made into a semi-solid composition.

That is, the gist of the present invention is a phosphoric acid ester system.

Chlorinated hydrocarbon type, polyglycol type, polyphenyl ether type, L-notate ester type, silicone oil type,
Consists of one or more oils selected from the group consisting of fluorinated hydrocarbons, phthalate esters, benzoic acid derivatives, and highly aromatic mineral oils, with a specific gravity (15/4°C) of 0.9
5 or more as a base oil, mixed with clay and fatty acid amide or wax, and is characterized by being a semi-solid that has a specific gravity heavier than water, is water-insoluble, non-emulsifiable, and exhibits thixotropic properties. It consists in a semi-solid composition for waterproofing.

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 carbonized oil such as chlorinated paraffin. Hydrogen type, polyglycol type such as polyoxypropylene glycol, polyoxybutylene glycol, nopolyphenyl ether type such as diphenyl ether, trimethylolpropane ester such as trimethylolpropane caprylic acid triester, trimethylolpropane oleate triester, and penta Hindered esters such as erythritol caprylic acid tetraester, pentaerythritol olein tetraester, and hentaerythritol ester, and methylphenyl silicone.

Silicone oil type such as dimethyl silicone.

Fluorinated hydrocarbons such as chlorofluorocarbons, chlorotrifluoroethylene polymerized oils, and tetrafluoroethylene polymerized oils, phthalate esters such as dimethyl phthalate and diptylphthalate, cyethylene glycol dibe/soate, Schif'o pyrene glycol dipene It consists of one or more selected from the group consisting of a benzoic reformed conductor such as dialkylene glycol shenzoate such as zoate, and highly aromatic mineral oil.

If the specific gravity (15/4℃) is about 0°95 or more, if the situation allows, the ratio! (15/4°C) of about 1.0 or more is used. The specific gravity is preferably as heavy as possible, but the specific gravity (15/
4℃) It is difficult to obtain those with a temperature exceeding about 1.5.

Clay and fatty acid amide or wax are used in combination as a thickening agent that imparts thixotropic properties and heat-resistant anti-sagging properties to the composition of the present invention.

Examples of clays include clay minerals that can form intercalation compounds, such as montmorillonite, nokuichi miculite, kaolinite, and /10 isite, which are used as a capital punishment. Although the clay may be unmodified, it is preferably modified to make it lipophilic clay. Lipophilic clay is, for example, published in Japanese Patent Publication No. 39-6216. 42-8697. Same 42-
19713, 43-14780, 47-13422
, 47-17143. 50-22565, 50-
25108 etc.'JK, aliphatic amine in clay,
It is modified by absorbing nitrogen-containing organic basic metals such as lipophilic cationic surfactants such as imidacillin and aminoamide, and nitrogen-containing resins such as aminoplast resin and polyepoxide resin. 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 are Dimethyldioctadecylamsonium iodide, dimethyldioctadecylammonium hydroxide, and dimethyldioctadecylammonium hydroxide, which can be obtained as an amine salt, or by reacting with an alkyl halide such as methyl iodide, or further reacting with an alkali such as potassium hydroxide. An example of imidacillin is 2-
Hebutadecenylimidazolyline, 2-octadecylimidacilline, 2-dodecylimidacilline, 4-octadecylimidazoli 7% 1-β-hydroxyethyl-2-heptadecylimidazoly/, 1-β-amino There are imidacilline compounds having about 10 to 22 carbon atoms in one molecule, which have a hydrocarbon group or a hydroxyalkyl group or an amino group as a substituent, such as ethyl-2-heptadecyl imidacilline. Examples of aminoamides include Diethylene triamine, polyalkylene polyamine such as polyethylene polyamine with a molecular weight of about 220 to 450, and about 1 per molecule of lauric acid, oleic acid, stearic acid, valmitic acid, etc.
Examples of aminoplast resins include cocondensates of the amines melamine and benzoguanamine, and examples of polyepoxide resins include reaction products with aliphatic monocarboxylic acids having 0 to 22 carbon atoms. Some are cured with organic amine curing agents. Clay can be added directly to the base oil and mixed to form a gel, but the clay can be mixed in advance with acetone, methyl ethyl ketone, or methanol.

Prepare a gel by adding it to a polar solvent such as ethanol, glopanol, ethylene glycol monomethyl ether, ethylene glycol hetanoethyl ether, diethylene glycol hetamine methyl ether, etc., then add this gel to the base oil and stir to complete the gelation. It is preferable to incorporate the polar solvent into the composition of the present invention by removing the polar solvent by heating at the same time. In order to further enhance the effect of the clay mineral as an intercalation compound and to enhance 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, which are condensates of these fatty acid amides and formaldehyde.
'-methylenebis fatty acid amide. These fatty acid amides may have about 14 to 44 carbon atoms in one molecule.

Examples of the wax include paraffin wax, carnauba wax, mineral wax such as Beadslok 1 synthetic wax, animal wax, vegetable wax, and base wax. The fatty acid amide and wax have a specific gravity (15/4°C) of about 0.90 or more, preferably about 0.9.
5 or more and a melting point of about 100° C. or more is preferable. Items with specific gravity (15/4℃) exceeding approximately 1.5, melting point approximately 1.
It is difficult to obtain products with temperatures exceeding 50°C. Specific gravity (15/4℃
) less than about 0.90 may separate from heavy base oils, and those with a melting point of less than about 100°C may have the ability to impart xyxotropy and anti-sag properties to the composition when used in combination with clay. Not enough. Fatty acid amide and wax may be used alone or both.

When clay is used in combination with fatty acid esterite or wax, thixotropic properties and anti-sag properties are imparted to the composition. The preferred content of clay is about 0.5 to 30 wt%, especially about 1
．． 0 to 10 wt% (based on the entire composition), and the preferred total amount of fatty acid amide or wax is about 0.5 to 40 wt%.
wt%, especially about 1.0 to 20 wt% (based on the total composition)
It is. clay.

If the amount of fatty acid amide or wax blended is too small, the viscosity will not increase and the anti-sagging properties will be low, and if the amount of these blended is too large, workability will deteriorate or the whole will solidify.

If necessary, antirust additives, antioxidants, lubricants (oil agents, load-bearing agents), etc. 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 such as abietic acid (colophonicum), 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 alkylphenol 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 penetrate into the water even when it comes into contact with water and remains in the composition, In soaps, monovalent metal salts and amine salts are undesirable because they dissolve in water.

Even in nonionic surfactants, the hydrophilic-lipophilic balance (
HLB) high 1, for example 4 or higher.

is highly soluble in water and is therefore undesirable. The preferred amount of these antirust additives is about 0.1 to 15 wt% (based on the total composition).

Examples of antioxidants include bisphenols, naphthylamines, zinc dialkyl dithio heptophosphates,
Ditertiary butyl alkylphenols, ketones
Amine condensates, benzo) IJ theazoles are used. The preferred amount of antioxidant is about 0.1 to 10 w
t% (based on the entire composition).

Examples of lubricants include tricresyl phosphate (which can also be used as a base oil), dipendyl disulfide, sulfur-treated olefins, and oleic acid. The preferred amount of lubricant is about 0.1 to 30 wt% (based on the total composition).

In order to provide the composition of the present invention with waterproof properties, the specific gravity of the composition must be higher than that of water or seawater. Specifically, the above base oil, thickener, and additives are selected so that the final composition has a specific gravity (at 1574°C) of about 1.02 or more, particularly about 1.04.
It is preferable to set it as above. The higher the specific gravity of the composition, the better.

Due to the availability of base oil and additives, the specific gravity (15/4°C) is approximately 1.
It is difficult to obtain compositions greater than 7. The use of the above-mentioned base oils also renders the final composition water-insoluble and non-emulsifying.

(Effects of the Invention) The semi-solid composition of the present invention exhibits xyxotropic properties and has excellent anti-sag properties, has a water stopping property (not replaced by water) since its specific gravity is heavier than water, is water-insoluble and has demulsifying properties, Excellent weather resistance. Also, since synthetic lubricating oil is used as the base oil, it has high load resistance.

There are also anti-rust properties (these can also be further increased by the use of additives). Therefore, the composition of the present invention is useful as a water-stopping semi-solid composition that can be applied to or filled into metal structures exposed to rainwater, wind damage, or in contact with water to protect the metal structures. Specific examples of applications include a water-stopping and rust-preventing lubricant for bridge iron movable bearings, and 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 in places where 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.

C’A example) Next, the present invention will be further explained by examples.

Examples 1 to 5 Waterproof semisolid compositions A, B, C, D according to the present invention from base oil % thickener and other additives.

E (referred to as Examples 1, 2, 3, and 4.5, respectively) were prepared. Its composition is as follows.

Base oil dimethyl phthalate45. Ow 1% (molecular weight 2000) Aromatic mineral oil (ratio! 15/4℃, 0.98) 10.0wt
% Thickener: Montmorillonite 4.0
1N, N'-methylene bisstearamide 8, O
I Additive: Rosin 7.0
#Tetraoxyethylene glycol tributyl, phenoyaete, 1·θ'' (Note) Montmorillonite is R oil-based montmorillonite modified by absorbing dimethyldioctadecylammonium hydroxide, and has a particle size of 05μ or less and a true specific gravity of 1.70. Example 2~
The same 9 used in 5. Composition B (Example 2) Base oil: dimethyl phthalate) 45.0
w t% polyoxyglopyre/glycol (molecular weight 2000) 25°0' aromatic ore/It
(Specific gravity 15/4°C 0.98) 10.0 #Thickening agent: Montmorillonite 5.0 #Stearamide 4. OI additive: rosin
10.0' Tetraoxyethylene glycol, Lipcha, Technique, Yanni fya l・01% base oil Ni diethylene glycol dipenzoate 50.0wt4 Aromatic mineral oil (specific gravity 15/4℃, 0.98) 24.0
#a death penalty somorillonite 5. O
#'Carnauba wax 10.0# Additive: Rosin 5. OI base oil: dimethyl phthalate) 40. Ow
t% trimethylolpropane caprylic,! ) IJ Eyu fya 36.0″ Tricresyl Phosphate) 10. O# Thickener:
Montmorillonite 4.0IN, Nl
-Methylenebisstearamide 4.0I 4.4'-butylidenebis(6-tert-butyl-3-methyl 1.Ow t% phenol) Composition E (Example 5) Base oil Nidimethyl 7-talate 23. Ow
t% pentaerythritol oleate tetraethylene 30・θ″ diphenyl ether 25.0 1 Thickening agent: Montmorillonite 5° OI polyethylene wax (molecular weight 3000, melting point 120°C, 10.0″ Additive: Rosin 5. OI tetraoxyethylene glycol trifle Tylphenol ether 1.0″ Trimethyldihydroquinoline 1.0 15j! Example 1~
Evaluation tests for Compositions A to No. 5 were conducted using the methods described in the following table.

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

From Table 2, Compositions A to E of Examples 1 to 5 are shown in Table 2 as semi-solids with a specific gravity heavier than water and have water stopping 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.

The base oil, which is the main component, is a synthetic lubricating oil, so it has good lubricity, and even if it falls into a river or sea, it sinks to the riverbed or seabed, so there are fewer 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 specific gravity (15/4°C).
is about 1.02 or more, viscosity is about 100,000 to 500,000P740
℃, approx. 50,000 to 250,000 CP760℃, anti-sagging property does not fall below the marked line, low temperature resistance, water resistance, and demulsification properties all pass, and rust prevention property does not rust for about 1000 hours or more in a wet test. Compositions A to E of Examples 1 to 5 are all suitable as a water-stopping and rust-preventing lubricant for bridge iron movable bearings because they are free from generation and have lubricity. 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.

[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, for reference. 1... Upper shoe, 2... Lower shoe, 3... Roller, 4... Receiver is plate, 5... Drain hole.

Claims (1)

[Claims] Phosphate ester type, chlorinated hydrocarbon type, polyglycol type, polyphenyl ether type, hindered ester type,
Contains one or more selected from the group consisting of silicone oils, fluorinated hydrocarbons, phthalate esters, benzoic acid derivatives, and highly aromatic mineral oils, and has a specific gravity (1
5/4℃) is 0.95 or more as a base oil, and clay and fatty acid amide or wax are blended with the base oil.The specific gravity is heavier than water, is water-insoluble, non-emulsifiable, and exhibits thixotropic properties. A semi-solid composition for water stopping, characterized in that it is semi-solid.