JPS5949247B2 - curable composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an emulsified bitumen/epoxy/unstructured hydraulic composition in which a cationic emulsifier or a nonionic emulsifier coexists therewith.

Conventionally, emulsified asphalt has been widely used in civil engineering and construction applications such as roads, bridges, railway construction, and building construction, as waterproofing materials, paving materials, filling injection materials, primers, moisture-proofing, corrosion-proofing, and coating materials.

In recent years, cement-asphalt mortars that combine the rigidity of cement and the flexibility of asphalt have been developed using cationic or nonionic emulsifiers and have come to be used, for example, as filling material for slab tracks.

However, in the case of emulsified asphalt, its adhesion to the underlying surface, water resistance, and alkali resistance are not necessarily sufficient.
Also, since it is water-based, it has the disadvantage that it is difficult to apply thickly. In addition, in order to improve this problem, a cement-asphalt mortar containing cement has been developed and is in practical use, but the stability of the emulsion system cannot be maintained because the emulsified asphalt is easily destroyed by mixing cement. Also, there are difficulties in terms of workability. The object of the present invention is to obtain a curable composition that does not have such drawbacks, improves the stability, workability, and physical properties of cement-asphalt systems, and has improved strength, chemical resistance, water resistance, and adhesiveness. As essential components, a bituminous substance A emulsified with a cationic emulsifier or a mixed emulsifier of this and a nonionic emulsifier, and a water-dispersible amide compound B containing an average of one or more amide groups per molecule, preferably contains a compound containing an imidazoline ring and an amide group, an epoxy compound C containing more than one epoxy group per molecule on average, and a hydraulic inorganic substance D,
If necessary, additional water E may be included.

Examples of emulsified bituminous materials in which cationic or nonionic and cationic emulsifiers coexist for use in the present invention include straight asphalt, cutback asphalt, propane deasphalted asphalt, blown asphalt, natural asphalt, tar pitch, petroleum pitch, and fatty acid pitch. , heavy mineral oil, and other bituminous substances alone or in combination of two or more.

Furthermore, in order to facilitate emulsification, although not necessarily necessary, plasticizers, pine oil, heavy oil, mineral oil, process oil, high boiling point solvents, fats and oils, fatty acids, naphthenic acid, rosin or its derivatives, etc. are mixed in advance. You can also use things. Among the emulsifiers necessary for the emulsification of the present invention, examples of cationic emulsifiers include alkylamines, amidoamines, imidazolines, N-alkyl-N-polyoxyethylene-N,N/-bisoxyethylenepropylene diamines, Aminated lignins, quaternary ammonium salts, etc. are used, and beef tallow alkylpropylene diamine salts are economically advantageous.

Among the organic amines mentioned above, the free amine type is generally used as a hydrochloride to form a water-soluble emulsifier, but acetates and nitrates can also be used. Nonionic emulsifiers include polyoxyethylene alkyl or nonyl phenyl ethers, polyoxyethylene fatty amines (
(weakly cationic) etc. can be used.

Further, in order to improve the storage stability of the emulsifier and adjust the viscosity of the system, calcium chloride, magnesium chloride, etc. can be added in an amount of about 0.1% by weight based on the emulsifier.

Emulsification may be carried out by a conventional method of dispersing the emulsifier and the bituminous material in the form of fine particles in water using a high-speed stirrer, homogenizer, or the like.

The water-dispersible imidazoline ring-containing amide compound B containing an average of one or more amide groups per molecule used in the present invention is a reaction in which an imidazoline ring is formed using a polyamine capable of forming an imidazoline ring. It is an imidazoline ring-containing amide compound obtained by reacting with a fatty acid, a dibasic acid, or a derivative thereof under certain conditions. Examples of imidazoline ring-forming polyamines include diethylenetriamine, triethylenetetramine, tetraethylenebentamine, pentaethylenehexamine, hexaethyleneheptamine, heptaethyleneoctamine, nonaethylenedecamine, and di-1,2-propanetriamine. Other diamines such as aminoethylethanolamine and aminoethylpropanolamine can also be used within the scope of the present invention.

In addition to the above polyamines, ethylenediamine, N-aminoethylbiperazine, etc. can be used as polyamines for forming water-dispersed amide.

On the other hand, examples of fatty acids or their derivatives include butyric acid, valeric acid, caproic acid, chifurylic acid, chipurinic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid,
Saturated fatty acids with carbon atoms of 4 or more, such as behenic acid, and their esters, tuccinic acid, linderic acid, lauroleic acid, tuzunic acid, fisetoleic acid, myristoleic acid, zomarinic acid, betroceric acid, oleic acid, elaidic acid, linoleic acid acids, linoelaidic acid, eleostearic acid, linoleic acid, parinaric acid, arachidonic acid and their esters, acrylic acid, methacrylic acid, maleic acid and their esters, tall oil fatty acids obtained from pulp manufacturing waste liquid and their esters, Examples include drying oils, semi-drying oils, or polymerized fatty acids such as dimer acids and trimer acids obtained by polymerizing these free fatty acids, and esters thereof.

Here, the above-mentioned drying oil or semi-drying oil includes soybean oil, linseed oil, tung oil, eno oil, cottonseed oil, sunflower oil, safflower oil, and dehydrated castor oil containing highly unsaturated fatty acids such as linoleic acid and linoleic acid. Examples include oil. Furthermore, polymers of acrylic acid and linoleic acid, saturated dibasic acids such as adipic acid, sebacic acid, and azelaic acid, esters of these acids, unsaturated linear dibasic acids, unsaturated branched dibasic acids, and esters of these can also be used. For example, the product name is DIAC.
ID-1550 (manufactured by Harima Kasei Kogyo Co., Ltd., trade name), 0
SK-DAUL-16 (trade name manufactured by Okamura Oil Co., Ltd.), 0
SK-DAUB-20 (same) and the like can also be used. These polyamines and fatty acids are mixed in a known molar ratio using a known method, for example, when forming an imidazoline ring, at normal pressure at 170 to 320°C, preferably at 250 to 290°C,
In addition, if the formation of an imidazoline ring is not particularly intended, the reaction may be carried out under normal pressure at 120 to 200°C, preferably 140 to 180°C, and both reactions can also be carried out at a lower reaction temperature by performing the reaction under reduced pressure. .

Furthermore, as fatty acids and/or derivatives thereof, it is preferable to use polymerized fatty acids or dibasic acids alone or mixtures of these with saturated fatty acids and unsaturated fatty acids. In the reaction with the above polyamine, the reaction temperature and reaction time are By appropriate adjustment, a compound containing a desired amide bond can be obtained.

Among the compounds containing an imidazoline ring and an amide bond, particularly preferred compounds contain an average of one or more imidazoline rings and an amide bond in one molecule, and an average of one or more primary and/or amide bonds in one molecule. It contains a secondary amino group. In addition, in order to further improve the compatibility and curability with emulsified asphalt, epoxy resin, and epoxy emulsion system, the above polyamide compound was
According to the description in Publication No. 17, acrylic acid, methacrylic acid or their esters, acrylonitrile, and/or an epoxy compound that is liquid at room temperature and has one or more adjacent epoxy groups in one molecule on average, and an amino bond. The active hydrogen atoms contained in the compound are contained in acrylic acid, methacrylic acid or their esters, acrylonitrile, and/or epoxy compounds that are liquid at room temperature and have one or more adjacent epoxy groups in one molecule on average. It is also possible to use a compound obtained by reacting in excess of the epoxy group.

The above epoxy compound used in the present invention (preferably as 0) has an average of one substituted or unsubstituted glycidyl ether group represented by the formula (where Z is a hydrogen atom, a methyl group, or an ethyl group) in the molecule. Epoxy resins having an average of more than one substituted or unsubstituted glycidyl ester group in the molecule represented by the formula (where Z is a hydrogen atom, a methyl group, or an ethyl group); These include epoxy resins having an average of more than one N-substituted or unsubstituted 1,2-epoxypropyl group in the molecule, where Z is a hydrogen atom, a methyl group, or an ethyl group.

A particularly preferable epoxy resin has an epoxy equivalent of 18
0 to 500 epoxy resin. The above-mentioned epoxy resins having more than one substituted or unsubstituted glycidyl ether group in the molecule include epoxy resins obtained by glycidyl etherification of phenolic hydroxyl groups and epoxy resins obtained by glycidyl etherification of alcoholic hydroxyl groups. Preferred examples of such epoxy resins include polyglycidyl ethers of polyhydric phenols having one or more aromatic nuclei and one or two aromatic nuclei.
Polyhydric phenol having more than 1 aromatic nucleus and 2 to 2 carbon atoms
Examples include polyglycidyl ethers of alcoholic polyhydroxyl compounds derived by addition reaction with four alkylene oxides.

Polyglycidyl ether is produced by, for example, reacting a polyhydric phenol having at least one aromatic nucleus with epihalohydrin in a conventional manner in the presence of a basic catalyst such as sodium hydroxide or a reactive amount of a basic compound. An epoxy resin containing such a polyglycidyl ether as a main reaction product, a polyhydric phenol having at least one aromatic nucleus, and shrimp halohydrin are reacted in the presence of an acidic catalyst such as boron trifluoride by a conventional method. An epoxy resin such as that obtained by reacting the obtained polyhalohydrin ether with a basic compound such as sodium hydroxide, or a polyhydric phenol having at least one aromatic nucleus and epihalohydrin is reacted with a basic catalyst such as triethylamine. It is an epoxy resin obtained by reacting a polyhalohydrin ether obtained by a conventional method with a basic compound such as sodium hydroxide in the presence of a catalytic amount of.

Similarly, polyglycidyl ether is a trifluorinated polyhydroxyl compound derived from an addition reaction between a polyhydric phenol having at least one aromatic nucleus and an alkylene oxide having 2 to 4 carbon atoms and epihalohydrin. The main reaction product is a polyglycidyl ether such as that obtained by reacting a polyhalohydrin ether obtained by a conventional method with a basic compound such as sodium hydroxide in the presence of an amount of an acidic catalyst such as boron. It is an epoxy resin.

The polyhydric phenols having at least one aromatic nucleus include mononuclear phenols having one aromatic nucleus and polynuclear polyhydric phenols having two or more aromatic nuclei.

Examples of such mononuclear polyhydric phenols include resorcinol, hydroquinone, pyrocatechol, phloroglycinol, 1,5-dihydroxynaphthalene, 2,
Examples include 7-dihydroxynaphthalene and 2,6-dihydroxynaphthalene.

Further, as an example of polynuclear polyhydric phenol, general formula [where Ar
is an aromatic divalent hydrocarbon such as naphthylene and phenylene, with phenylene being preferred for purposes of this invention.

Y' and Y, may be the same or different, and include a methyl group, n-propyl group, n-butyl group, n-hexyl group,
Alkyl groups, preferably with up to 4 carbon atoms, such as n-octyl, or halogen atoms, i.e. chlorine, bromine, iodine or fluorine, or methoxy, methoxymethyl, ethoxy, ethoxyethyl groups , n-butoxy, amyloxy, preferably those having up to 4 carbon atoms. When a substituent other than a hydroxyl group is present on either or both of the above-mentioned aromatic divalent hydrocarbon groups, these substituents may be the same or different. m and z are 0 that react with the number of hydrogen atoms in the aromatic ring Ar that can be substituted with a substituent.
An integer with a value from (zero) to a maximum value, which can be the same or different values. R, for example, 1C-, -0-
, -S-, -SO-, -SO2-, or alkylene groups such as methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, 2
- Ethylhexamethylene group, octamethylene group, nonamethylene group, decamethylene group or alkylidene group, such as ethylidene group, propylidene group, isopropylidene group, isobutylidene group, amylidene group, isoamylidene group, 1-phenylethylidene group or cycloaliphatic group For example, 1,4-cyclohexylene group, 1,3-cyclohexylene group, cyclohexylidene group, halogenated alkylene group, halogenated alkylidene group, halogenated cycloaliphatic group, or alkoxy mono and aryloxy Mono-substituted alkylidene groups or mono-alkoxy and aryloxy-substituted alkylene groups or mono-alkoxy and aryloxy-substituted cycloaliphatic groups such as methoxymethylene, ethoxymethylene, ethoxyethylene, 2-ethoxytrimethylene group, 3-ethoxypentamethylene group, 1,4-(2-
methoxycyclohexane) group, phenoxyethylene group,
2-phenoxytrimethylene group, 1,3-(2-phenoxycyclohexane) group or alkylene group such as phenylethylene group, 2-phenyltrimethylene group, 1,7
-phenylpentamethylene group, 2-phenyldecamethylene group or aromatic group such as phenylene group, naphthylene group or halogenated aromatic group such as 1,4-(2-
chlorophenylene) groups, 1,4-(2-fluorophenylene) groups or alkoxy- and aryloxy-substituted aromatic groups such as 1,4-(2-methoxyphenylene)
group, 1,4-(2-ethoxyphenylene) group, 1,4-
(2-n-propoxyphenylene) group, 1,4(2-phenoxyphenylene) group or alkyl-substituted aromatic group such as 1,4-(2-methylphenylene) group, 1,
4-(2-ethylphenylene) group, 1,4-(2-n-
A divalent group such as a divalent hydrocarbon group such as a propylphenylene) group, a 1,4-(2-n-butylphenylene) group, or a 1,4-(2-n-dodecylphenylene) group, Alternatively, R1 can be a ring fused to one of the above Ar groups, as is the case in the compound of the formula, or R1 can be a polyethoxy group, a polypropoxy group, a polythioethoxy group, a polybutoxy group, It can also be a polyalkoxy group, such as a polyphenylethoxy group, or R1 can be a group containing a silicon atom, such as a polydimethylsiloxy group, a polydiphenylsiloxy group, a polymethylphenylsiloxy group. , or R1 can be an aromatic ring, a tertiary amino ether bond, a carbonyl group, or two or more alkylene or alkylidene groups separated by a sulfur or sulfur-containing bond such as a sulfoxide. ] There is a polynuclear divalent phenol represented by

Among these polynuclear divalent phenols, particularly preferred are those having the general formula (wherein Y' and Y1 have the same meanings as above, m and z have a value of 0 to 4, and R1 preferably has a value of 1 to 3. It is a polynuclear dihydric phenol represented by an alkylene group or an alkylidene group or a saturated group represented by the formula or U2 having 5 carbon atoms.

Examples of such dihydric phenols include 2,2-bis(p-hydroxyphenyl)-propane, commonly referred to by the trade name bisphenol A, 2,4'-dihydroxydiphenylmethane, bis-(2- hydroxyphenyl)-methane, bis-(4-hydroxyphenyl-methane, bis-(4-
Hydroxy-2,6-dimethyl-3-methoxyphenyl)-methane, 1,1-bis-(4-hydroxyphenyl)-ethane, 1,2-bis-(4-hydroxyphenyl)monoethane, 1 , 1-bis-(4-hydroxy-2-chlorophenyl) monoethane, 1,1-bis-(3,5-dimethyl-4-hydroxyphenyl) monoethane, 1,3-
Bis-(3-methyl-4-hydroxyphenyl)-propane, 2,2/bis(3,5-dichloro-4-hydroxyphenylpropane, 2,2-bis(3-phenyl-4
-hydroxyphenyl)-propane, 2,2-bis-(
3-isopropyl-4-hydroxyphenyl)-propane, 2,2-bis-(20isopropyl4-hydroxyphenyl)-propane, 2,2-bis-(4-hydroxynaphthyl)-propane, 2,2- Bis-(4-hydroxyphenyl)-pentane, 3,3-bis-(4-hydroxyphenyl)-pentane, 2,2-bis-(4-hydroxyphenyl)-heptane, bis-(4-hydroxy phenyl)methane, bis-(4-hydroxyphenyl)-cyclohexylmethane, 1,2-bis(4-hydroxyphenyl)-1,2-bis-(phenyl)-propane, 2,2-bis-( 4-hydroxyphenyl)-1
- bis-(hydroxyphenyl)alkanes such as phenylpropane or 4,47-dihydroxybiphenyl,
2,2'-dihydroxybiphenyl, dihydroxybiphenyl such as 2,4/-dihydroxyphenyl or bis-1(4-hydroxyphenyl)-sulfone, 2,4'
-dihydroxydiphenylsulfone, chloro-2,4-
Dihydroxydiphenyl sulfone, 5-chloro-4,4
'-dihydroxydiphenylsulfone, 3'-chloro-
di-(hydroxyphenyl)-sulfone such as 4,4/-dihydroxydiphenyl sulfone or bis-(4-
hydroxyphenyl) monoether, 4,3'-(or 4
, 2'-1- or 2,2'-dihydroxy-diphenyl) ether, 4,4'-dihydroxy-2,6-dimethyldiphenyl ether, bis-(4-hydroxy-3-isobutylphenyl) ether, bis -(4-hydroxy-3-isopropylphenyl)-ether, bis-(4
-hydroxy-3-chlorophenyl) monoether, bis(4-hydroxy-3-fluorophenyl) monoether, bis(4-hydroxy-3-promphenyl) monoether, bis(4-hydroxynaphthyl) monoether, Bis-(4-hydroxy-3-chlornaphthyl)-ether, bis-(2-hydroxybiphenyl)-ether, 4,4'-dihydroxy-2,6-dimethoxydiphenyl ether, 4,4'-dihydroxy -2,5-
Includes di-(hydroxyphenyl)-ethers such as diethoxydiphenyl ether, and also 1,1-bis-(
4-hydroxyphenyl)-2-phenyl)-2-phenylethane, 193,3-trimethyl-1-(4-hydroxyphenyl)-6-hydroxyendane, 2,4-
Bis-(p-hydroxyphenyl)-4-methylpentane is also suitable.

Furthermore, another preferred group of polynuclear divalent phenols has the general formula (where R3 is a methyl or ethyl group, R2 is an alkylidene group having 1 to 9 carbon atoms or other alkylene group, p is represented by O~4), such as 1,4-bis-(4-hydroxybenzyl)-benzene, 1,4-bis-(4-hydroxybenzyl)-tetramethylbenzene, 1,4-bis- Examples include (4-hydroxybenzyl)tetraethylbenzene, 1,4-bis-(p-hydrokingmyl)-benzene, and 1,3-bis(p-hydrokingmyl)-benzene.

Other polynuclear polyvalent phenols include:
For example, initial condensates of phenols and carbonyl compounds (e.g., phenolic resin initial condensates, condensation reaction products of phenol and acrolein, condensation reaction products of phenol and glyoxal, condensation reaction products of phenol and pentanediallyl, Condensation reaction products of resorcinol and acetone, initial condensation products of xylene-phenol-formalin), condensation products of phenols and polychloromethylated aromatic compounds (e.g. condensation products of phenol and bischloromethylxylene), etc. can be mentioned.

Therefore, a polyhydroxyl compound is a compound obtained by reacting the above-mentioned polyhydric phenol having at least one aromatic nucleus with an alkylene oxide in the presence of a catalyst that promotes the reaction between the 0H group and the epoxy group. -ROH bound to the phenol residue by an ether linkage obtained at least
(wherein R is an alkylene group derived from alkylene oxide) or (and) -(RO)NH (where R is an alkylene group derived from alkylene oxide and one polyoxyalkylene chain contains different alkylene groups) You can stay there.

n is a compound having an atomic group (2 or an integer of 2 or more indicating the number of polymerized oxyalkylene groups). In this case, the ratio of the polyhydric phenol and alkylene oxide is 1:
The ratio of alkylene oxide to OH groups of the polyhydric phenol is preferably 1:1 to 10, preferably 1:1 to 3 (equivalent: equivalent). Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, etc., but when these react with the polyhydric phenol to form an ether bond, those that generate side chains are particularly preferred, and such alkylene oxides can be used. Among these, propylene oxide, 1,2-butylene oxide, and 2,3-butylene oxide are preferred, with propylene oxide being particularly preferred.

A particularly preferred group of such polyhydroxyl compounds has the general formula (Y/, Xl, m, z and R1
is the same as that of the above formula, R is an alkylene group having 2 to 4 carbon atoms, and n1 and N2 have values of 1 to 3).

Furthermore, another preferred group of polyhydroxyl compounds has the general formula (wherein R, , R2, and R3 are the same as those in the above formula, and R is an alkylene group having 2 to 4 carbon atoms. , N, and N2 are values of 1 to 3).

In addition, epihalohydrin is represented by the general formula (where Z is a hydrogen atom, a methyl group, or an ethyl group, and Muhydrin, 1,2-epoxy-2-methyl-3-chloropropane, 1,2-epoxy-2-ethyl-3-chloropropane, and the like.

The acidic catalyst that promotes the reaction between the epihalohydrin and the polyhydric phenol or polyhydroxyl compound includes:
Lewis acids such as boron trifluoride, stannic chloride, zinc chloride, and ferric chloride, derivatives exhibiting these activities (e.g. boron trifluoride-ether complex compounds), or mixtures thereof can be used. I can do it. Similarly, basic catalysts that promote the reaction between epihalohydrin and polyhydric phenol include alkali metal hydroxides (e.g. sodium hydroxide), alkali metal alcoholades (e.g. sodium ethylate), tertiary amine compounds (e.g. : triethylamine, triethanolamine), quaternary ammonium compounds (e.g., tetramethylammonium bromide), or mixtures thereof, thus producing glycidyl ether simultaneously with the reaction, or Examples of basic compounds that can be used to ring-close the halohydrin ether produced as a result of the dehydrohalogenation reaction to produce glycidyl ether include alkali metal hydroxides (e.g., sodium hydroxide), alkali metal aluminates (e.g., : sodium aluminate) etc. are conveniently used. These catalysts or basic compounds can be used as they are, or with suitable inorganic or
and) Of course, it can be used as an organic solvent solution.

Epoxy resins having more than one substituted or unsubstituted glycidyl ester group in the molecule include polyglycidyl esters of aliphatic polycarboxylic acids or aromatic polycarboxylic acids, for example, Also included are epoxy resins obtained by polymerizing glycidyl methacrylate synthesized from the epihalohydrin shown and methacrylic acid. Also, N-substituted or unsubstituted 1,2-
An example of an epoxy resin having an average of more than one epoxypropyl group in the molecule is an epoxy resin obtained from an aromatic amine (for example, aniline or aniline having an alkyl substituent in the nucleus) and an epihalohydrin represented by the above general formula. , an initial condensate of an aromatic amine and an aldehyde (
Examples include epoxy resins obtained from aniline-formaldehyde initial condensate, aniline-phenol formaldehyde initial condensate) and epihalohydrin.

In addition, conventionally known epoxy resins such as the various epoxy resins described in "Manufacture and Application of Epoxy Resins" (edited by Hiroshi Kakiuchi) may be used. Further, in the composition of the present invention, an epoxy compound emulsified in water can also be used, and such an emulsified epoxy compound can be obtained by emulsifying the above-mentioned epoxy compound with a nonionic emulsifier.

Particularly preferred nonionic emulsifiers include block polymers of ethylene oxide and propylene oxide (for example, Pluronic F-68 manufactured by Asahi Denka Kogyo) and ethylene oxide high adducts of nonylphenol. Emulsification is preferably carried out using a homogenizer or high-speed stirrer, and if necessary, in addition to water, for example, toluene, xylene, esters, alcohols,
Solvents such as ketones, mineral spirits, ethylene glycol monomethyl ether, and ethylene glycol monomethyl ether acetate may also be added.

It is also possible to emulsify by adding a diluent such as DBP, DOP, furfuryl alcohol, tetrahydrofurfuryl alcohol, benzyl alcohol, etc. to lower the viscosity.
Further, particularly when emulsifying a solid epoxy compound, a method of adding toluene, xylene, etc. to liquefy and emulsify is preferred from the viewpoint of workability. Hydraulic inorganic substances that are essential components of the composition of the present invention include, for example, Portland cement,
Various cements such as blast furnace cement, silica cement, fly ash cement, white cement, alumina cement, and various types of cement are used.

The proportions of each essential component used in the composition of the present invention are approximately as follows. That is, the water-dispersible amide compound B and the epoxy compound C should be kept in a substantially equivalent relationship since the former acts as a curing agent for the latter, but this need not be so strict. Furthermore, the bituminous material and hydraulic inorganic material D can be changed depending on the application and required performance, but the approximate usage ratio is the sum of the water-dispersible amide compound B and epoxy compound C to the weight part of the emulsified bituminous material AlOO. Amount (solid content) 1-200
Part by weight preferably 10 to 100 parts by weight, hydraulic inorganic material D
The amount is 1 to 400 parts by weight, preferably 50 to 250 parts by weight. Also, the mixing ratio of water is arbitrary, but if it is too small, emulsification will not be possible, while if it is too large, it will not have a positive effect on hardening properties, transportation costs, containers, etc. About 1000% by weight is realistic.

When the composition of the present invention is actually used, pigments such as titanium oxide and red iron oxide, fillers such as calcium carbonate, talc, silica, and clay mica, crushed stone or coarse aggregate, and the like are added to the above-mentioned essential components.

In addition, plasticizers such as white tar, xylene resin, and biphenyl may be added for the purpose of improving workability and reducing costs. Examples of the present invention are shown below, but the present invention is not limited thereto.

Note that parts in the examples are based on weight. Example 1 1 mole of tall oil fatty acid and 1 mole of pentaethylenehexamine.
8 parts of acetic acid was added to 120 parts of a compound (I) having an imidazoline ring and an amide group obtained from 3 moles of the compound, and 80 parts of hot water was added little by little to cationize the compound.

11.6 parts of this cationized compound were mixed with 58.7 parts of molten straight asphalt in a high speed stirrer.
At a temperature of 0 to 75°C, 29.7 parts of warm water is added little by little while stirring to obtain a cationic emulsified asphalt. 74 parts of this cationic emulsified asphalt, 7 parts of a compound having an upper imidazoline ring and an amide group, ACR-epoxy emulsion EM-1-60 (trade name, manufactured by ACR),
Non-ionic emulsion of bisphenol liquid epoxy resin with epoxy equivalent weight 190, solid content 60%) 25
Department, Portland Semen Day 00 copies, Silica Sand No. 6 200 copies,
20 parts of water was mixed and hardened. The bending strength after 3 weeks is 3
At 5 kg/Cd, it was superior to 19 kg/Cflt when no epoxy emulsion was included.

In a chemical resistance test using a 10% sodium hydroxide drop test, the surface of the material not containing epoxy emulsion was eroded and eroded, but the surface of the material of the present invention had no abnormality.

Example 2 1 mole of tall oil fatty acid and 1 mole of pentaethylenehexamine.
3 moles were reacted at 140 to 150°C for 3 hours to obtain a water-dispersible amide compound having an amide group.

20 parts of butyl glycidyl ether (epoxy equivalent: 170) was added to 100 parts of this amide compound, and the reaction was carried out at 100°C for 2 hours to obtain an epoxy-added amide compound. To 6 parts of this epoxy-added amide compound or the amide compound before addition of epoxy, 74 parts of the same cationic emulsified asphalt used in Example 1, 15 parts of ACR-epoxy emulsion EM-1-60, and 10 parts of Portland cement.
0 parts and 15 parts of water were added thereto and cured for one day.

The bending strength after one month is 36k for epoxy-added amide.
9/CfLl The other one is 32k9/d and the one without epoxy emulsion is 20kg/? It was hot.

In addition, in the 10(f) NaOH dropping test, there was no abnormality on the surface of the sample of the present invention, but the surface of the sample without epoxy emulsion turned white. Example 3 Polymerized fatty acid Versadime 216 (manufactured by Henkel Japan) 1
00 parts, tall oil fatty acid 100 parts, triethylenetetramine 70 parts, pentaethylenehexamine 90 parts 140 parts
The reaction was carried out at ~150°C for 3 hours to obtain a water-dispersed polyamide having amide groups.

5 parts of this polyamide, 40 parts of the cationic emulsified asphalt used in Example 1, and ACR-epoxy emulsion E.
M-1-6015 part, α-type gypsum (manufactured by Ube Industries, Ltd.)
100 parts and 30 parts of water were added and cured for one month. The bending strength was 381<g/d and 26k9/d without the addition of epoxy emulsion.

Water resistance was also tested by dropping water, but the surface of the product of the present invention turned white. Example 4 Nitsusan Asfazole Shoichi 20 (manufactured by Nissan Chemical, cationic emulsifier, amine value 290-3201) in 99 parts of warm water
acid value 5 or less, softening point 34-37°C) 0.6 part, hydrochloric acid (P
0.5 part of H-2.3) and 0.5 part of calcium chloride were added and heated to 50 to 60°C to obtain a yellow transparent liquid.

Claims (1)

[Claims] 1 Emulsified bituminous material A emulsified with a cationic emulsifier or this and a nonionic emulsifier, water-dispersible imidazoline ring-containing amide compound B containing an average of one or more amide groups per molecule, an average of 1 per molecule A curable composition containing as essential components an epoxy compound C containing more than 3 epoxy groups, a hydraulic inorganic substance D and, if necessary, additional water E.