JPS5822051B2 - Curable bituminous composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a curable bituminous composition suitable for waterproofing materials, anti-corrosion coatings, fillers, binders and the like.

Bitumen has been used for waterproofing materials for a long time due to its superior performance, availability, economy, etc., and even now it accounts for the majority of all waterproofing materials used.

Waterproofing methods that use bituminous materials usually include heating and melting bituminous materials such as blown asphalt, catalytic blown asphalt, asphalt compound, rubberized asphalt, and coal tar pitch on site, and applying or pouring this onto the waterproofing base. The so-called heating membrane construction method is used to adhere roof inks and laminate them to form a waterproof layer.

Alternatively, a waterproof sheet that has been processed into a sheet at a factory by covering a reinforcing material such as non-woven fabric, mesh cloth, paper, etc. with heat-melted rubber asphalt as a core material is pasted onto the waterproof base with adhesive, or A sheet waterproofing method is also used in which the back side of the tarpaulin sheet and the waterproof base are heated with a burner, etc., and the rubberized asphalt of the tarpaulin sheet is applied while being heated and melted.

However, heating membrane method Q'! Although the layering of bituminous material and roof ink has the advantage of highly reliable waterproof performance, the temperature at which the bituminous material is melted and used is 20°C.
The temperature is over 0 degrees Celsius, and there is a risk of fire entering the melting pot that melts the bituminous material, as well as bad odor and smoke.
The reality is that there are many problems with construction in urban areas because of the pollution generated and the risk of burns to workers during transportation and waterproofing work.

In addition, the sheet waterproofing method has difficulty in workability, and furthermore, the sheet cannot be sufficiently bonded to the waterproof base, leaving a gap between the waterproof base and the sheet, which tends to cause blistering.

Furthermore, the adhesive method has the disadvantage that there is a risk of the adhesive solvent igniting due to fire, and that heating with a burner consumes a large amount of fuel.

In order to improve the shortcomings of the heating waterproofing method, an imperial waterproofing method using asphalt emulsion as its main ingredient has been developed in recent years.

In other words, these cold construction methods involve applying an asphalt emulsion containing rubber such as styrene-butadiene rubber or chloroprene rubber as is and forming a waterproof membrane by air drying, or using an emulsion breaker rubber such as an aqueous calcium chloride solution. This is a method in which the asphalt emulsion is sprayed together with the asphalt emulsion to forcibly destroy the asphalt emulsion and harden to form a film in a short period of time.

However, these construction methods also have major problems.

First, the air-drying film-forming mechanism is extremely affected by temperature (drying is slow in the winter, hardening takes many days, and in the summer the surface moisture evaporates too quickly, causing the surface It has the disadvantage of causing a skinning phenomenon and accompanying blistering.

In addition, in the process of spraying an emulsion breaker such as calcium chloride at the same time as the asphalt emulsion to instantly destroy the asphalt agent and separate the asphalt from the water to form a film, we also improve adhesion to the substrate and treatment of free water. However, the actual situation is that it has the disadvantage of requiring an expensive spraying machine and skill for construction.

Furthermore, as an imperial waterproofing method, Japanese Patent Publication No. 50-7617 proposes a waterproofing method using an elastic bitumen material, which is a combination of a hydrophilic urethane resin having an isocyanate group at the end and an asphalt emulsion.

However, this construction method cures quickly and requires a special spraying machine for construction, and the performance of the waterproof membrane obtained is that it foams a lot and has poor water resistance, alkali resistance, and
It has the disadvantage that it is not sufficient in terms of durability, etc.

The present inventors have overcome the drawbacks such as sloping in the currently used waterproofing materials mainly made of bituminous materials and their construction methods, and have developed waterproofing materials that utilize the advantages of bituminous materials and provide excellent performance using metal construction. As a result of intensive research to obtain wood,
The present invention has been completed.

The object of the present invention is to provide a metal-work type waterproofing material which overcomes the drawbacks such as sloping, and a metal-work type curable bituminous composition suitable for corrosion-resistant coatings, fillers, and bonding materials.

The present invention uses component A consisting of a urethane prepolymer having terminal isocyanate groups obtained by reacting an organic polyisocyanate with a polyoxyalkylene polyol having an average molecular weight of 1,000 to 20,000 and an ethylene oxide content of 20% by weight or less, and bitumen. In the emulsion, (a) 2 to 80% by weight of either cement or lime or a mixture of both based on the bitumen emulsion, and (0) 2 with an average molecular weight of 50 to 5000 bonded to the incyanate group in component A.
Component B consists of a special bitumen emulsion containing an 8-functional organic active hydrogen compound in an amount of 0.1 to 1 equivalent to the equivalent of isocyanate (NGO) in component A, and these components A and B are combined. The present invention relates to a curable bituminous composition characterized in that it is formed by mixing.

In the present invention, the urethane prepolymer having terminal incyanate groups (hereinafter simply referred to as urethane prepolymer) constituting component A is propylene glycol, glycerin, ethylene glycol, trimethylolpropane,
Average molecular weight 1000-20 obtained by addition polymerizing alkylene oxides such as propylene oxide, ethylene oxide, butylene oxide, styrene oxide, etc. to polyhydric alcohols such as pentaerythritol and sorbitol.
2 to 000 with an ethylene oxide content of 20% by weight or less
Organic polyisocyanate such as tolylene diisocyanate (TD
I), diphenylmethane diynyanate (MDI polymethylene polyphenylisocyanate, naphthalene diisonanate, xylylene diisocyanate, hexamethylene diisocyanate, trinoenylmethane triisocyanate, hydrogen softened TDI, hydrogen softened MDI, isophorone diisocyanate, etc.) It is a urethane prepolymer having a terminal incyanate group obtained by reacting one or a mixture thereof.

Generally, the reaction equivalent ratio NGO10H of polyisocyanate to polyol is preferably 1.5 to 4, preferably 2 to 30, and urethane prepolymers containing 2.5 to 6% by weight of free isocyanate are preferred.

Since this urethane prepolymer has an ethylene oxide content of hydrophilic groups of 0 to 20% by weight, it is generally insoluble in water, and the urethane prepolymer alone is not dispersed in water.

It is also possible to add small amounts of solvents that do not react with isocyanates, such as methyl ethyl ketone, methyl isobutyl ketone, doluol, xytol, etc., to the urethane prepolymer.

The bitumen emulsion used in the present invention is a bitumen mixture of one or more of straight asphalt, blown asphalt, cutback asphalt, petroleum asphalt such as propane asphalt, heavy oil, natural asphalt, tar, pitch, etc. The substance can be treated with various surfactants such as anionic, cationic, nonionic, and amphoteric, one or more emulsifiers such as clay (e.g. bentonite), alkalis, acids, salts, dispersants, protective colloids, etc. A bitumen emulsion is emulsified in water using a suitable emulsifier such as a colloid mill, homogenizer, or homomixer.

All of these bituminous emulsions contain cement, lime 1. Good miscibility is required when mixing cement and lime mixtures.

Even if cationic emulsions can be mixed with cement, lime, etc., the emulsions tend to separate if mixed for many days.

Therefore, it is better not to use cationic emulsions unless they are used immediately after mixing.

Typical bituminous emulsions include asphalt emulsions made by emulsifying straight asphalt with a penetration degree (at 250°C) of about 30 to 350, and emulsifying mixtures of coal tar and coal tar pitch. There is a tar emulsion.

In the bitumen emulsion, known bituminous emulsification techniques such as a bitumen emulsifier, a substance used for emulsification, and a bitumen emulsification method are used.

For example, a typical emulsification method involves heating and melting a bituminous material into a liquid state and mixing it with an emulsion prepared by dissolving an emulsifier and other substances in water through an emulsifying machine.

At this time, part of the emulsifier may be added to the bitumen.

Examples of emulsifiers for anionic bituminous emulsions include alkali salts of vinylizole resin (product name of Percules, a type of resin acid), higher alcohol sulfate esters, alkylaryl alphonates, alkylbenzene sulfonates, α-olefin sulfonate, higher alcohol ethoxylate, higher alcohol ethoxylate sulfate, alkyl sulfate, alkali salt of casein, alkaline lignin salt, lignin sulfonate, polyacrylic acid, soap, resinate, naphthalene sulfonate ,
Examples include allylnaphthalene sulfonate.

In addition, nonionic surfactants, amphoteric surfactants, bentonite, etc. are also used in combination.

Examples of emulsifiers for nonionic bituminous emulsions include alkylene oxides (ethylene oxide or mainly composed of ethylene oxide) such as alkylphenope alcohols, fatty acids, fatty amines, fatty amides, and fatty amidoamines.
There are additional additions.

Anionic surfactants, amphoteric surfactants, weak cationic surfactants, and bentonite are also used in combination.

Bentonite is used as an emulsifier for clay-type bitumen emulsions.

Various surfactants are also used in combination.

Examples of dispersants and protective colloids include sodium naphthalene sulfonate, sodium allylnaphthalene sulfonate,
Casein, alginic acid, gelatin, carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose, polyvinyl alcohol, sodium polyacrylate, polyvinyl pyrrolidone, lignin sulfonate, alkali lignin sulfonate, nitrofumate, condensed phosphate, etc. There is.

In addition, the bitumen emulsion used in the present invention includes natural rubber, synthetic rubber (for example, styrene-butadiene rubber, styrene-isoprene rubber, imprene rubber, butadiene rubber, chloroprene rubber, nitrile rubber, butyl rubber, halogenated butyl rubber, chlorinated polyethylene rubber,
ethylene propylene rubber, styrene butadiene block polymer rubber, styrene isoprene block polymer rubber, etc.),
Synthetic polymer resins (e.g. ethylene vinyl acetate copolymer, ethyl acrylate copolymer, polyacrylate, polyvinyl chloride, etc.), synthetic resins (e.g. coumaron resin, petroleum resin, xylene resin, synthetic terpene shugebi alkyd resin, etc.) ), natural resins (rodin and its derivatives, terpene resins, etc.), etc. to emulsify bituminous materials in water.

Further, bituminous emulsions used in the present invention include those obtained by adding latexes and emulsions such as natural rubber, synthetic rubber, synthetic polymer phase fJ bacteria synthetic resin, and natural resin to the above-mentioned bituminous emulsions.

All of these bituminous emulsions also require good miscibility when mixed with cement, lime, etc.

Furthermore, oil and gas process oils, plasticizers, fatty acids, resin acids, fatty amines, It is anti-aging and can also contain solvents and other substances.

Furthermore, urethane prepolymer catalysts such as zinc octylate, dibutyltin dilaurate, zinc acetate, sodium silicate, trimethylamine, and lower amine compounds, methyl ethyl ketone, xylene, toluene, mineral salt, and cellosolve are added to the various bitumen emulsions mentioned above. Solvents such as, viscosity modifiers, anti-aging agents for improving heat resistance and aging resistance, etc. can also be blended.

The bituminous emulsion used in the present invention usually has an evaporation residue of 50
A concentration of ~70% by weight is used, but it is also possible to use one with a lighter or higher concentration than this.

The bituminous emulsion used in the present invention must not only be able to mix fillers such as cement and lime, but also be able to mix a crosslinking agent of urethane prepolymer, and for this purpose, if necessary, it must be able to contain surfactants. Agents, dispersants, anti-caking agents, protective colloids, and other substances may also be added.

Cement, lime, or a mixture of both (hereinafter simply referred to as cement, etc.) used in the present invention includes Portland cement, fly ash cement, blast furnace cement, blast furnace colloidal cement, colloidal cement, silica cement, sulfate-resistant cement, and alumina cement. It is one or a mixture of two or more of cement such as cement and lime such as quicklime and slaked lime.

Cement and the like are mixed with the bitumen emulsion in a range of 2 to 80% by weight.

The presence of cement or the like prevents foaming caused by the reaction between the urethane prepolymer and water when mixing the A and B components of the curable bitumen composition of the present invention, facilitates the dispersion and mixing of the A component into the B component, and This has the effect of creating a homogeneous mixture and also creating a non-foamed mixture when the mixture is cured.

This is thought to be because when the isocyanate of the urethane prepolymer reacts with water, it generates carbon dioxide gas, but this carbon dioxide gas is absorbed and captured as calcium-based salts such as calcium carbonate without generating it as gas. It will be done.

When the amount of bitumen emulsion such as cement used is less than 2% by weight based on the bitumen emulsion, the foaming prevention effect may not be sufficient.

On the other hand, when it exceeds 80% by weight, the foaming prevention effect is sufficient, but there is a risk that water absorption increases and waterproofness decreases.

Magnesia, magnesium hydroxide, carbon, graphite, other calcium carbonate, clay, talc, and other fillers can be used together with cement and the like.

Anti-coagulation or agglomeration agents are used to mix cement, etc. into bituminous emulsions and keep them stable over long periods of time without coagulation or agglomeration.

Among cements and the like, especially when using cement, coagulation or agglomeration is likely to occur due to hydration reaction, so it is necessary to use a coagulation or agglomeration inhibitor.

It can also be omitted with lime.

Also, it can be omitted when cement is mixed immediately before use.

Anti-coagulation or aggregation agents (hereinafter referred to as anti-coagulation agents) used in the present invention include sugars, sugar alcohols, hydroxycarboxylic acids and their salts, and other substances.

These include, for example, sugars such as sucrose, glucose, fructose, lactose, canctose, xylose, maltose, mannose, ribose, arabinose, sugar alcohols such as mannitol and sorbitol, gluconic acid, galactonic acid, glucuronic acid, tartaric acid, and the like. Acid salts, pyrogallol, gallic acid, catechol, etc., ligninsulfonic acid and its salts, alkalinigenin and its salts,
These include humic acid, nitrofumic acid, and their salts.

The amount of these anti-caking agents, etc. is 090% relative to the amount of cement, etc.
It is used in a proportion of 1 to 2% by weight.

The effect of these anti-coagulation agents is to prevent coagulation and sedimentation during the storage period when cement, etc. are mixed into the bitumen emulsion, or to re-disperse the cement, etc. by simple stirring even if it has partially settled. In addition, it is believed that it helps the mixing of components A and B, controls the reaction of the urethane prepolymer with water, and facilitates the reaction between the urethane prepolymer and the organic active hydrogen compound. .

The average molecular weight bonded to the incyanate group in component A is 5
0 to 50000 2 to 8 functional organic active hydrogen compounds (hereinafter simply referred to as active hydrogen compounds) are 10H in the molecule.
It is an organic compound containing an active hydrogen group that can bond with a group, -NF2 group, >NH group, -8H group, -COOH group, and has an average molecular weight of 50 to 5000 and is 2 to 8 functional. be.

Specifically, the average molecular weight of 4,4'methylenebis(2-chloroaniline), mono-, di-, or triethanolamine, morpholine, ethylenediamine, toluenediaminodiphenylmethane, and polypropylene glycol is 400 to
2,000 and polypropylene triol with an average molecular weight of 600 to 50,000, amines such as polymeric amine compounds in which the OH group at the end of the molecule is substituted with NF2 group, and these amines, aniline, ammonia, etc., propylene oxide, ethylene oxide, butylene oxide, styrene. These are amine polyols with an average molecular weight of 50 to 500,000 and 2 to 8 functional groups obtained by addition polymerization of alkylene oxides such as oxides.

Additionally, mono-, di-, and triethylene glycols, mono-,
Polyhydric alcohols such as di- or tripropylene glycol, 1-4 butanediol, 1,6-hexanediol, glycerin, trimethylolpropane, pentaerythritol-diglycerin, sorbitol, sucrose, and propylene oxide, ethylene oxide, butylene oxide. Polyethers and polyols having an average molecular weight of 50 to 50000 and 2 to 8 functionalities prepared by addition polymerization of , styrene oxide, etc. can also be used as active hydrogen compounds.

The amount of these active hydrogen compounds added to the bitumen emulsion is such that the total equivalent of amine groups or hydroxyl groups, or both, is 0.1 to 1.0 to 1.1 to 1.0.
It is used in an amount of 0 equivalent, preferably 0.4 to 0.6 equivalent.

Active hydrogen compounds including these amine compounds are
When component A and component B are mixed, they preferentially react with isocyanate groups to form urea bonds or urethane bonds, resulting in an elastic cured product that is non-foaming and has excellent mechanical properties without generating carbon dioxide gas. obtained, which is more advantageous for the purpose of the present invention.

The special bitumen emulsion of component B is made by mixing a bitumen emulsion with cement, etc., an anti-caking agent, etc., and an active hydrogen compound.

The mixture may be mixed at room temperature using a suitable stirring device.

Although the mixing order can be freely selected, dispersion of the cement etc. can be made easier by mixing the active hydrogen compound, anti-caking agent, etc. with the bitumen emulsion and then mixing the cement etc.

The curable bituminous material of the present invention is obtained by mixing component A and component B.

Since the pot life of the mixture is short, mixing is carried out immediately before use.

The blending ratio of A component and B component is A:B (weight ratio) 1:4
This blending ratio is within the range of ~2:1 and is appropriately selected depending on the use, purpose, etc.

As a waterproofing agent, it is usually preferable to have a ratio of 1:2 to 1:1.

The curable bitumen composition of the present invention is usually supplied in a two-component form, consisting of a urethane prepolymer as component A, and a bitumen emulsion mixed with component B such as cement, an anti-caking agent, and an active hydrogen compound.

When used, component A and component B are mixed at a predetermined mixing ratio, and the mixture is used before it hardens.

This mixture can be made into a uniform homogeneous mixture by simple stirring without using any special equipment.

If mixing is somewhat difficult due to a large proportion of component A, it is advisable to add a small amount of water to component B before mixing the two.

It is generally preferable that Component B is mixed in advance, but in special cases, for example, when a bitumen emulsion for mixing cationic cement is used, each of the ingredients of Component B may be mixed immediately before use. It is also possible to prepare component B by mixing them, and then use the mixture of component A and component B.

A mixture of component A and component B at a predetermined mixing ratio is liquid and has good workability in flow coating, brush coating, spraying, etc. at room temperature.

It also has good leveling properties when applied to a base for waterproofing, etc.

Furthermore, instead of mixing the A and B components in advance before use, the A and B components may be sprayed from separate nozzles and applied using a device that mixes the two at the tip of the nozzle.

The curable bitumen composition of the present invention, which is a mixture of component A and component B in a predetermined proportion, has a pot life of 5 to 40 minutes, although it depends on the formulation, and usually has a pot life of 10 minutes or more. If too long, the urethane prepolymer reacts with water and the active hydrogen compound, causing the entire body to harden into an elastic body.

It becomes tack-free 3 to 24 hours after curing.

When curing begins, most of the bituminous emulsion decomposes, and over time, it completely decomposes, crosslinking of the polyurethane resin progresses, and due to evaporation of water, the bituminous material and cement, etc. are homogeneously dispersed in the polyurethane resin elastic network structure. and combine to form an integrated composite cured body.

This cured product is non-foaming with almost no foaming caused by carbon dioxide gas, and has excellent mechanical properties, water resistance, alkali resistance, chemical resistance, weather resistance, etc.

The characteristics and effects of the curable bitumen composition of the present invention are summarized as follows.

(1) The curable bitumen composition of the present invention hardly causes foaming from the mixing process of mixing components A and B until curing and even after curing.

Due to the presence of cement, etc. in component B, carbon dioxide gas generated by the reaction between the urethane prepolymer of component A and water,
It is thought that foaming does not occur because it is absorbed without being generated as gas.

In addition, cement, etc., together with anti-caking agents, etc., control this reaction and further promote the reaction between the urethane prepolymer and the active hydrogen compound, which is thought to further suppress foaming. (2) Pot life is relatively long. Long lasting and good workability.

Longer pot life than the combination of bituminous emulsion and hydrophilic urethane resin (water-soluble urethane prepolymer).

The reason for this is that the urethane prepolymer of component A is not water-soluble (because it is dispersed and mixed in the aqueous phase of the bitumen emulsion in an emulsified state by the emulsifier of the bituminous emulsion of component B, the amount of urethane prepolymer in component A is higher than that of the water-soluble one). Since physical contact between the incyanate group and the water and active basic compound in component B takes time, the reaction becomes slow.

Furthermore, the pot life is slightly extended by the emulsifier itself in the bitumen emulsion, and the presence of cement and anti-caking agents control the reaction between the urethane prepolymer and water, and the active hydrogen compound and This is thought to be because the reaction occurs preferentially.

Because of this, the pot life is relatively short, making it easier to work with.

Furthermore, since the active hydrogen compound is present in component B, the leveling properties and fluidity when applying or pouring the curable bitumen composition of the present invention are improved.

(3) The cured product has excellent mechanical properties, water resistance, alkali resistance, chemical resistance, weather resistance, etc.

Cured product made from a combination of bituminous emulsion and hydrophilic urethane resin (water-soluble urethane prepolymer) (Japanese Patent Publication No. 50-761
No. 7) had the disadvantage that the cured product did not have sufficient water resistance, alkali resistance, etc. because the urethane resin contained a large amount of hydrophilic ethylene oxide chains.

Furthermore, the mechanical properties were also insufficient.

The present invention uses a specific urethane prepolymer that is insoluble in water, which is different from the conventional method, and reacts only with water (and reacts with active hydrogen compounds) due to the presence of cement, anti-caking agent, etc. Crosslinking of polyurethane resin, to make
This is thought to be due to the progress of polymerization, which combines the reticulated polyurethane resin with excellent physical properties with bitumen, cement, etc., to form a composite cured product.

(4) It can be applied at room temperature and there is no need to use fire.

Since the curable bituminous composition of the present invention has the characteristics and effects of sloping, it can be effectively used for waterproofing materials, corrosion-resistant coatings, fillers, binding materials, and the like.

For example, in the case of waterproof materials, it is possible to apply waterproofing materials by brushing, pouring, spraying, etc. on a waterproof base, and also to apply non-woven fabrics, woven fabrics, reticulated fabrics, nets, paper, etc. It is also possible to perform membrane-type waterproofing by using a bituminized core material of these materials and pasting them with the curable bitumen composition of the present invention.

In addition, as a corrosion-resistant coating material, it can be used, for example, to protect steel plates, wooden plates, etc. for vehicles, containers, and the like.

Furthermore, the filler ' can also be used to waterproof the joints of structures, for example.

In addition, as a binder, for example, aggregate, rubber powder, cork powder, etc. can be mixed to make an elastic pavement body.

The curable bitumen composition of the present invention can be expected to develop new uses by selecting various bituminous emulsions and urethane prepolymers.

The present invention will be specifically described below with reference to Examples, but the present invention is not limited to these Examples.

The materials and test methods used in the Examples and Comparative Examples are as follows.

1. Component A Urethane prepolymer (1) A-100; average molecular weight 300002 - trifunctional mixed polyether polyol (ethylene oxide chain content 20% by weight) and toluene diisocyanate (TDI
).

Free NGO 3.7% by weight (2) A-150; Polyadduct of TDI and polyether polyol (ethylene oxide chain content: 5% by weight) having an average molecular weight of 300,002 to 3-functional mixture.

3.0% by weight of free NCO (3) A-200; Polyadduct of TDI and polyether polyol (no ethylene oxide chain content) having an average molecular weight of 350,002 to 3 functional mixtures.

Free NGO 6.0% by weight. (4) X-100; Polyadduct of average molecular weight 300,002 to trifunctional polyether polyol (ethylene oxide chain content: 60% by weight) and TDI.

6.4% by weight of free NGO. 2. 8 ingredients (1) Asphalt emulsion and tar emulsion used in bituminous emulsion (1) Asphalt emulsion (anionic type) Emulsifier Higher alcohol sulfate ester, sodium alkylbenzene sulfonate.

Evaporation residue 58% by weight, penetration of evaporation residue (25℃
) 185 (2) Asphalt emulsion (nonionic) Emulsifier Ethylene oxide adduct of nonylphenol.

Evaporation residue 60% by weight, penetration of evaporation residue (25℃
)98 (3) Asphalt emulsion (anionic/nonionic) Emulsifier Sodium alkylbenzenesulfonate, ethylene oxide adduct of nonylphenol.

Evaporation residue 55% by weight, penetration of evaporation residue (25℃
)96 (4) Asphalt emulsion (cationic) JIS K2208 MK-3 equivalent, emulsifier quaternary salt of ethylene oxide adduct of fatty diamine, etc.

Evaporation residue 60% by weight, penetration of evaporation residue (25°) 48 (5) Asphalt emulsion (claytive) Straight asphalt is emulsified using bentonite or other emulsifier.

Evaporation residue: 55% by weight, moisture: 45% by weight (6) Coal tar pitch emulsion (claytive) A mixture of coal tar pitch and coal tar is emulsified using bentonite and other ingredients as milk.

Evaporation residue 55% by weight, moisture 45% by weight (2) Rubber latex and synthetic polymer emulsion used for bitumen emulsion (L) SBR; styrene-butadiene rubber latex, non-volatile content 45% by weight (2) EVA ; Ethylene vinyl acetate copolymer emulsion, nonvolatile content 55% by weight (3) Inorganic filler such as cement and lime (1) Portland cement; ordinary Portland cement (2) Slaked lime; Industrial slaked lime (3) Quicklime; Industrial quicklime (4) Calcium carbonate; limestone powder (4) Anticaking agents, etc. (1) Sucrose (Sug) (2) Sodium gluconate (GS) (3) Sodium ligninsulfonate (L, 5) (4
) Tulbitol (SO) (5) D-arabinose (Ar) (5) Active hydrogen compound (L) T-4; Toluenediamine (2.4/2.
6 isomer ratio 80/20), hydroxyl equivalent 84.5 (2) E-4; amine polyol prepared by addition polymerizing ethylene oxide and propylene oxide to ethylenediamine, hydroxyl equivalent 68.4 (3) TEA; ) Liethanolamine (4) ML-1so; Liquid amine in which 50% of 4,4'methylenebis(2-chloroaniline) is dissolved in a plasticizer, amine equivalent 66.75 (5) J-400 ; A polymeric diamine in which the terminal OH group of polyoxypropylene glycol having an average molecular weight of 400 is replaced with an NH2 group.

Amine equivalent 200 (6) 1-4BuOH; 1 4-butanediol 3
, Test method and evaluation (1) Storage stability of component B Component B was left at a constant temperature of 40°C for one month, and if no coagulation or aggregation of the inorganic filler was observed, or even if sedimentation was observed, it could be checked by simple stirring. Those that are easily dispersed are marked as ○, and those that are not easily dispersed are marked as ×.

(2) Mixing and coating workability The mixed system of component A and B has low viscosity, has good leveling properties, and can be applied even 10 minutes after mixing.
, the reverse of this was set as ×.

(3) Coating film performance (1) Mechanical properties: Based on urethane rubber test according to JIS-A-6021.

Cured coating films with hardness (Shore A) of 30 to 60, tensile strength of 15 kg/l or more, elongation of 300% or more, and tear strength of 8 kg/cIrL or more were rated as ○, and those with less than this were rated as x.

(2) Water resistance: The cured coating film was immersed in water at room temperature for 60 days, and those with no swelling or deformation and water absorption of 20% or less were rated as ○, and those that did not meet this were rated as ×.

(3) Alkali resistance: The cured coating film was immersed in a Ca(OH)2 saturated aqueous solution at room temperature for 60 days, and the water absorption rate was 2.
If it is 0% or less, it is marked as ○, and if it does not meet this, it is marked as ×.

Example 1 Component B is prepared by mixing bitumen emulsion with ordinary Portland cement, lime, etc., calcium carbonate, coagulation or sedimentation prevention agent, active hydrogen compound, etc. in the proportions shown in Table 1.

Weigh and mix component A and component B in the proportions shown in Table-1,
A curable bituminous composition of the invention was obtained.

The mixing state and coating workability of this curable bituminous material were investigated, and the foaming state (bubbles) during curing, surface adhesion (tack), tensile strength,
Mechanical properties such as elongation and tear strength, water resistance, and alkali resistance were tested.

Separately, component B was tested for storage stability.

The results of these tests are shown in Table-1.

With the mixing ratio shown in Table 1, the B component of the mixing ratio of Example 1 is mixed with no cement, lime, etc., and the B component of the comparative example is mixed with cement, lime, etc. but does not contain an active hydrogen compound. It was prepared and mixed with the same component A as in Example 1, and tested in the same manner as in Example 1.

In addition, a comparison was made in which the A component was a water-soluble urethane prepolymer, the same B component as in Example 1 was selected, the A component and the B component were mixed, and the test was conducted in the same manner as in Example 1.

These results are summarized in Table 1.

Example 2 On the ground of an agricultural reservoir that was well-developed and finished with fir pressure,
A layer of polyester non-woven fabric is laid down as closely as possible with as few gaps as possible and fixed using U-shaped wires, and on top of this the curable bitumen composition of the present invention (prescribed in Experiment A1 of Example 1) is applied per 1 m. It was applied at a rate of about 3 liters and cured to waterproof the reservoir.

After application, water was poured and stored from the 7th month onward.

Even after a year has passed, it remains highly waterproof, with no water leaks, and is still fully functioning as a water reservoir.

Comparative examples include Experiment 7 A, 2' 1 and A, 2 of Example 1.
' Even when applying 2, it hardens quickly and does not form a uniform coating, and the waterproof layer is blistered and swells due to its poor water resistance, making it unable to fulfill its role of water storage. Ta.

Example 3 The hardening bituminous composition of the present invention according to the experimental version of Example 1 and the 3 formulations was applied to the reinforced concrete structure base of the roof of a reinforced concrete building according to the Architectural Institute of Japan Standard Specifications for Building Works J.
ASS 8 Waterproofed by applying PU-4 specification for waterproofing to a thickness of 2 dragons.

There were no abnormalities even after one year (the waterproofing effect was fully demonstrated.

For comparison, the material according to the recipe 4-1 of Example 1 was applied to a waterproof base having the same structure as in the above example to make it waterproof.
After a year had passed, cracks appeared in the waterproof layer on some of the rising corners and on the cracks in the base, causing defects in the waterproof layer.

Example 4 Clay type coal tar pitch emulsion (evaporation residue 5
After adding and mixing 0.02 parts by weight of sucrose and 3 parts by weight of active hydrogen compound E-4 to 100 parts by weight (5% by weight), 20 parts by weight of ordinary Portland cement was added and mixed,
Component B of the curable bitumen composition of the present invention is prepared.

The storage stability of this B component is good.

A curable bituminous composition of the present invention could be obtained by using urethane prepolymer A-100 as component A and mixing 50 parts by weight of component A and 60 parts by weight of component B.

This product had a pot life of 10 minutes or more, good coating workability, and good physical properties of the cured product.

This was used to waterproof the roof of a reinforced concrete building, and a waterproof coating made of a non-foamed elastic material with good adhesion to the underlying concrete surface was obtained.

This waterproof coating film had excellent waterproof properties and good weather resistance after one year, and exhibited its waterproofing effect without any abnormalities.

Example 5 Clay asphalt emulsion (evaporation residue 55% by weight)
) To 100 parts by weight were added 0.1 parts by weight of sucrose and 3.8 parts by weight of active hydrogen compound T-4, and to this were added 10 parts by weight of ordinary Portland cement, 5 parts by weight of slaked lime,
Component B of the curable composition of the present invention is prepared by adding and mixing 10 parts by weight of calcium carbonate powder.

The storage stability of this B component is good.

A curable bituminous composition of the present invention could be obtained by using urethane prepolymer A-100 as component A and mixing 50 parts by weight of component A and 60 parts by weight of component B.

This material can be used as a waterproof material as in Example 4, has a long pot life, is easy to work with, and forms a non-foamed elastic waterproof coating.

Excellent adhesion to waterproof substrates, good water resistance and weather resistance,
Demonstrates excellent waterproofing effect.

Claims (1)

[Claims] 1 A component consisting of a urethane prepolymer having terminal isocyanate groups obtained by reacting an organic polyisocyanate with a polyoxyalkylene polyol having an average molecular weight of 1000 to 20000 and an ethylene oxide content of 20% by weight or less, and a bituminous emulsion. @) 2 to 80% by weight of cement, lime, or a mixture of both based on the bitumen emulsion; The hydrogen compound is added to the isocyanate in component A (
1. A curable bitumen composition comprising a component B consisting of a special bitumen emulsion containing 0.1 to 1 equivalent relative to the equivalent of NGO), and a mixture of component A and component B.