JPS5936930B2 - Curable epoxy resin composition - Google Patents

Description

[Detailed description of the invention] The present invention relates to curable epoxy resin compositions.

The composition of epoxy resin and asphalt is for road paving,
In recent years, development and study have been progressing as a waterproofing agent, but the biggest bottleneck is the poor compatibility of the epoxy resin and active organic curing agent with asphalt. For example, ``Petroleum and Petrochemicals'' Vol. 20, No. 5, p. 49 states, ``The key point of all the above-mentioned efforts is that polyepoxy can be easily mixed into a homogeneous composition with asphalt material or coal tar pitch. The inability to do so seems like a headache." In order to solve such compatibility problems, methods such as adding additives or using modified asphalt have been considered, but no method that is fully satisfactory is known yet.

As a result of intensive research to solve the above problems, the present inventors have developed a new asphalt-containing polyepoxide curable composition with improved epoxy/asphalt system compatibility by adopting a new epoxy resin curing agent. They discovered that a product can be obtained and completed the present invention. It is an object of the present invention to provide a polyepoxy curable composition that has excellent compatibility with asphalt.

The curable epoxy resin composition of the present invention contains, as essential components, (]) an epoxy resin having more than VCI adjacent epoxy groups per molecule on average, (2) a compound having both an imidazoline ring and an amide bond ( ■-1) and/or the compound (■-1) and the compound (■-2) having one or more epoxy groups in one molecule, so that the active hydrogen of the compound (■-1) is attached to the epoxy group. The reacted product (■-3) and Tsukuda asphalt are contained in such a proportion as to be in excess.

The epoxy resin (I) used in the present invention has the formula
Epoxy resin having an average of more than one substituted or unsubstituted glycidiether group in the molecule, represented by ZCH2-C-CH2-O- N\/' (where Z is a hydrogen atom, methyl group, or ethyl group) (-1), an epoxy resin 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) (-2), a formula ( This includes epoxy resins (1-3) 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. It will be done.

The epoxy resin (1-1) having more than one substituted or unsubstituted glycidyl ether group in the molecule is an epoxy resin obtained by glycidyl etherification of a phenolic hydroxyl group and a glycidyl etherification of an alcoholic hydroxyl group. Preferred examples of such epoxy resins (1-1) include polyglycidyl ethers of polyhydric phenols having one or more aromatic nuclei (1-1-1), 1 piece or two
Polyhydric phenol having more than 1 aromatic nucleus and 2 to 2 carbon atoms
Polyglycidyl ethers of alcoholic polyhydroxyl compounds (1-1-2) derived by addition reaction with four alkylene oxides or polyglycidyl ethers of aliphatic polyhydroxyl compounds containing no nucleus (1-1) -3) etc.

However, polyglycidyl ether (1-1-1) is
For example, polyglycidyl ethers such as those obtained by reacting polyhydric phenol A having at least one aromatic nucleus and epihalohydrin B by a conventional method in the presence of a basic catalyst such as sodium hydroxide or a reaction amount of a basic compound. A polyhydrin obtained by reacting an epoxy resin containing as a main reaction product or a polyhydric phenol A having at least one aromatic nucleus with shrimp halohydrin B in a conventional manner in the presence of a catalytic amount of a basic catalyst such as triethylamine. It is an epoxy resin obtained by reacting phosphorus ether with a basic compound such as sodium hydroxide.

Similarly, polyglycidyl ether (1-1-2) or polyglycidyl ether (1-1-3) is, for example, a polyhydric phenol having at least one aromatic nucleus and a carbon number of 2.
Polyhydroxyl compound B derived by addition reaction with ~4 alkylene oxides or aliphatic polyhydroxyl compound C without a nucleus and epi-mouth hydrin B
The main reaction produces a polyglycidyl ether such as that obtained by reacting a polyhalohydrin ether with a basic compound such as sodium hydroxide by a conventional method in the presence of an acidic catalyst amount such as boron trifluoride. It is an epoxy resin that is included as a product.

Here, the polyvalent phenol A having at least one aromatic nucleus includes a mononuclear polyvalent phenol (A-1) having one aromatic nucleus and a polynuclear polyvalent phenol having two or more aromatic nuclei. There is (A-2).

Examples of such mononuclear polyhydric phenols (A-1) include resorcinol, hydroxine, pyrocatechol, phloroglucinol, 1,5-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, etc. can be mentioned.

Examples of the polynuclear polyhydric phenol (A-2) include the general formula [wherein Ar is an aromatic divalent hydrocarbon such as a naphthylene group and a phenylene group, and a phenylene group is preferred for the purpose of the present invention.

Y' and Y1 may be the same or different, and are methyl group, rhopropyl group, n-butyl group, n-hexynyl group, n
- an alkyl group such as an octyl group, or a halogen atom, such as a chlorine atom, a bromine atom, an iodine atom, or a fluorine atom, or an alkoxy group such as a methoxy group, a methoxymethyl group, an ethoxy group, an ethoxyethyl group, an n-butoxy group, or an amylmexy group; Preferably it is an alkoxy group having up to 4 carbon atoms. If either or both of the above aromatic divalent hydrocarbon groups has a substituent other than a hydroxyl group! In IC, these substituents may be the same or different. m and z are integers having a value from O (zero) to the maximum value corresponding to the number of hydrogen atoms in the aromatic ring (Ar) that can be substituted by a substituent,
They can be the same or different values. For example, R1 is
'R, -0-, -s- -SO-, -SO2-Ro1 (S
).

- (n is an integer of 2 to 6) or an alkylene group such as a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a 2-ethylhexamethylene group, a metamethylene group, a nonamethylene group,
Decamethylene group or alkylidene group such as ethylidene group, lopylidene group, isopropylidene group, isoptylidene group, amylidene group, isoamylidene group, 1-phenylethylidene group, ω-(halogenated synclopentanenyl) alkylidene group or cycloaliphatic group such as 1 ,4-
Cyclohexylene group, 1,3-cyclohexylene group, cyclohexylidene group or ') halogenated alkylene group or halogenated alkylidene group or halogenated cycloaliphatic group or alkoxy mono- and aryl-mono-substituted an alkylidene group or an alkoxy- and aryloxy-substituted alkylene group, or an alkoxy- and aryloxy-substituted cycloaliphatic group such as a methoxymethylene group, an ethoxymethylene group, an ethoxyethylene group, a 2-ethoxytrimethylene group ,
3-ethoxypentamethylene group, 1,4-(2-methoxycyclohexane) group, phenoxyethylene group, 2-phenoxytrimethylene group, 1,3-(2-phenoxycyclohexane) group or alkylene group, e.g. 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) group, 1,4-(2-fluorophenylene)
groups or alkoxy- and aryloxy-substituted aromatic groups such as 1,4-(2-methoxyphenylene) groups, 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-propylphenylene) group, 1,4-(2-n-butylphenylene) group, 1,4-(2-n-dodecylphenylene) group, A group represented by the formula (R is a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms), a group represented by the formula (wherein R2 is a hydrogen atom or a hydrocarbon group optionally substituted with a hydroxyl group or an epoxy group) R1 can be a divalent group such as a divalent hydrocarbon group, or R1 can be a ring fused to one of the Ar groups, as in the case of the compound represented by the formula 0H/. , or R can also be a polyalkoxy group such as polyethoxy, polypropoxy, polythioethoxy, polybutoxy, polyphenylethoxy, or R1 can be, for example, polydimethylsiloxy, polydiphenylsiloxy. , may be a group containing a silicon atom such as a polymethylphenylsiloxy group, or R may be an aromatic ring, a tertiary amino group, an ether bond, a carbonyl group or a sulfur-containing bond such as sulfur or sulfoxide. polynuclear dihydric phenols, which can be two or more alkylene or alkylidene groups separated by

Among these polynuclear divalent phenols, particularly preferred are:
General formula (wherein Y' and Y1 have the same meanings as above,
m and z are values of 0 to 4, and R1 is preferably 1 to 3.
an alkylene group or an alkylidezo group having 4 carbon atoms,
-SO2-, -0-, or a saturated group represented by the formula, Q
is 0 or 1).

Examples of such dihydric phenols include 2,2-bis-(4-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-pis(4-hydroxyphenyl)ethane, 1
, 2-bis(4-hydroxyphenyl)ethane, 1,1
-Bis(4-hydroxy-2-chlorophenyl)ethane, 1,1-bis(3,5-dimethyl-4-hydroxyphenyl)ethane, 1,3-bis(3-methyl-4-hydroxyphenyl)propane , 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane, 2,2-
Bis(3-phenyl-4-hydroxyphenyl)propane, 2,2-bis(3-isopropyl-4-hydroxyphenyl)propane, 2,2-bis(2-isopropyl-4-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)hebutane, bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)cyclohexylmethane, 1,2-bis(4- hydroxyphenyl)-1,2-bis(phenyl)propane, 2,2
-Bis(hydroxyphenyl) alkanes such as -bis(4-hydroxyphenyl)-1-phenylproban or 4,4'-dihydroxybiphenyl, 4,4'-dihydroxyoctachlorobiphenyl, 2,2'-dihydroxy biphenyl, dihydroxybiphenyl or bis-(4-hydroxyphenyl) sulfone such as 2,4'-dihydroxybiphenyl, 2,4'-dihydroxydiphenyl sulfone, chloro-2,4-dihydroxydiphenyl sulfone, Di(hydroxyphenyl) such as 5-chloro-4,4'-dihydroxydiphenylsulfone, 3'-chloro-4,4'-dihydroxydiphenylsulfone
Sulfone or bis(4-hydroxyphenyl) ether, 4,3'-(or 4,2'-1- or 2,2'-dihydroxydiphenyl) ether, 4,4'-dihydroxy-2,6-dimethyldiphenyl Ether, bis(4-hydroxy-3-isobutylphenyl) ether, pis(4-hydroxy-3-isopropylphenyl) ether, bis(4-hydroxy-3-chlorophenyl) ether, bis(4-hydroxy-3 -Chlorphenyl) ether, bis(4-hydroxy-3-fluorophenyl) ether, pis(4-hydroxy-3-promphenyl) ether, bis(4-hydroxynaphthyl) ether, bis(4-hydroxy-3-chlornaphthyl) ) ether, bis(2-hydroxybiphenyl)ether, 4
, 4'-dihydroxy-2,6-dimethoxydiphenyl ether, 4,4'-dihydroxy-2,5-diethoxydiphenyl ether; (4-hydroxyphenyl)-2-phenylethane, 1,3,3-trimethyl-1-(4-hydroxyphenyl)-6-hydroxyindan, 2,4-bis(p-hydroxyphenyl)-4
-Methylbentane is also suitable.

Furthermore, another preferred group of such polynuclear divalent phenols has the general formula (where R3 is a methyl or ethyl group, R1 and R2 are an alkylidene group having 1 to 9 carbon atoms or other alkylene group, p 0 to 4), such as 1,4-bis(4-hydroxybenzyl)benzene, 1,4-bis(4-hydroxybenzyl)tetramethylbenzene, 1,4-bis(4-hydroxybenzyl) ) tetraethylbenzene, 1,4-bis(p-hydrokingmyl)benzene, 1,3-bis(p-hydrokingmyl)benzene, and the like.

Other polynuclear polyhydric phenols (A-2) include, for example, initial condensates of 1,1,2,2-tetrakis(4-hydroxyphenyl)ethanephenols and carbonyl compounds (e.g. Phenol resin initial condensate, condensation reaction product of phenol and acrolein, condensation reaction product of phenol and glyoxal, condensation reaction product of phenol and bentane diallyl, condensation reaction product of resorcinol and acetone, xylene-phenol (formalin initial condensate), condensation reaction products of phenols and polychloromethylated aromatic compounds (eg, condensation reaction products of phenol and bischloromethylxylene), and the like.

Therefore, the polyhydroxyl compound B is a compound obtained by reacting the above-mentioned polyhydric phenol A 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. - which is bound to the phenol residue by an ether bond obtained at least
ROH (here R is an alkylene group derived from alkylene oxide) or (and) -(RO)NH (here R
is an alkylene group derived from alkylene oxide, and one polyoxyalkylene chain may contain different alkylene groups. 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 A and alkylene oxide is 1:1 (molar remolar) or more,
Preferably, the ratio of alkylene oxide to the polyhydric phenol AOOH group is 1:1 to 10, preferably 1
:1-10, preferably 021:1-3 (equivalent: equivalent). Examples of the alkylene oxide here include ethylene oxide, propylene oxide, butylene oxide, etc., but those that generate side chains when reacting with the polyhydric phenol A to form an ether bond are particularly preferred, and such alkylene oxides Examples of such polyhydroxyl compounds B include propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 1,3-butylene oxide, and 1,3-butylene oxide, with propylene oxide being particularly preferred. A particularly preferable group of compounds has the general formula (wherein, . It is a polyhydroxyl compound represented by four alkylene groups, n1 and N2 having values of 1 to 3).

Furthermore, another preferred group of such polyhydroxyl compounds has the general formula (wherein Rl, R2, R3
and p is the same as that of the above formula (A-2-1-2), R is an alkylene group having 2 to 4 carbon atoms, and n1 and N2 have values of 1 to 3). It is.

Other examples of the polyhydroxyl compound B containing a nucleus include alicyclic polyols obtained by hydrogenating the aromatic nucleus of the polyhydroxyl compound A.

In addition, examples of the aliphatic polyhydric compound C which does not contain a nucleus include polyhydric alcohols such as ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, dibutylene glycol, glycerin, and pentaerystol; Polyhydric polyhydroxy compounds such as polyhydric alcohols or other active hydrogen-containing compounds (for example, compounds with groups such as amino groups, carpoxyl groups, thiohydroxyl groups, etc.) with alkylene oxides, polyether polyols, etc. Examples include compounds. In addition, the above-mentioned epihalohydrin b herein refers to the general z formula
) (where z is a hydrogen atom, a methyl group, an ethyl group, and X5 is a halogen atom), and examples of such epihalohydrin b include epichlorohydrin, epipromhydrin, 1,2-epoxy -2-methyl-3-chloropropane, 1,2-epoxy-2-ethyl-3-chloropropane, and the like.

As the acidic catalyst that promotes the reaction between shrimp halohydrin B and polyhydroxyl compound B or polyhydroxyl compound C, Lewis acids such as boron trifluoride, stannic chloride, zinc chloride, and ferric chloride can be used. Derivatives shown (
For example, boron trifluoride-ether complex compound) or a mixture thereof can be used.

Similarly, basic catalysts that promote the reaction between shrimp halohydrin B and polyhydric phenol A include alkali metal hydroxides (e.g., sodium hydroxide), alkali metal alcoholades (e.g., sodium ethylate), and tertiary amines. compounds (e.g., triethylamine, triethanolamine), quaternary ammonium compounds (e.g., tetramethylammonium bromide), or mixtures thereof, can be used to simultaneously produce glycidyl ether or Examples of basic compounds that generate glycidyl ether by ring-closing the halohydrin ether produced as a result of the dehydrogenation reaction include alkali metal hydroxides (e.g., sodium hydroxide) and alkali metal aluminates. (Example: Sodium aluminate)
etc. are conveniently used.

Of course, these catalysts and basic compounds can be used as they are or as a solution in an appropriate inorganic or/and organic solvent.

In addition, the epoxy resin (1-2) VC having on average one or more substituted or unsubstituted glycidyl ester groups in its molecule may be an aliphatic polycarboxylic acid or an aromatic polycarboxylic acid (e.g. phthalic acid, isophthalic acid, terephthalic acid, Tetrahydrophthalic acid, methyltetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, maleic acid, phthalic acid, itaconic acid,
Succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sepacic acid, dimer fatty acid, trimellitic acid, trimesic acid, pyromellitic acid, cyclobentanetetracarboxylic acid, these...Rogge 7-substituted compounds There are also polyglycidyl esters (including terminal carboxyl polyester oligomers obtained from these polyhydric carboxylic acids and polyhydric alcohols), for example, polyglycidyl esters synthesized from epihalohydrin b represented by the above general formula and methacrylic acid. Also included are epoxy resins such as those obtained by polymerizing glycidyl methacrylate. In addition, epoxy resins having an average of more than one N-substituted or unsubstituted 1p2-epoxypropyl group in the molecule (
Examples of 1-3) include epoxy resins obtained from aromatic amines (e.g. aniline or anilines having an alkyl substituent in the nucleus) and epihalohydrin b represented by the above general formula, and initial condensation of aromatic amines and aldehydes. Examples include epoxy resins obtained from a compound (for example, aniline-formaldehyde initial condensate, aniline-phenol-formaldehyde initial condensate) and epihalodrine b.

Other epoxy resins include epoxidized oils (e.g., epoxidized linseed oil, epoxidized soybean oil, epoxidized safflower oil, epoxidized tung oil, epoxidized eno oil, epoxidized dehydrated castor oil, epoxidized oiticica oil, epoxidized tall oil, etc.), epoxidized fatty acids, epoxidized cyclic olefin compounds {e.g., vinylcyclohexene dihydroxide, 1-(1-methyl-1,2-epoxyethyl)-3,4-epoxy-4-methylcyclohexane, 3
, 4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarpoxylate, 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarpoxylate, bis(
3,4-epoxy-6-methylcyclohexylmethyl)
adipate, synchropentane edge oxide, dibentene dioxide, tetrahydroindene dioxide, or these rings are first B in general formula (A-2-1).
1, other compounds such as Araldite CY-175 (product name of Ciba Corporation), epoxidized products of conjugated diene polymers (e.g., epoxidized polyprotadiene, epoxidized styrene-butadiene) Copolymers, epoxidized acrylonitrile-styrene copolymers) epoxidized products of polymers containing unsaturated bonds (e.g. epoxidized polypropylene, epoxidized polyisoptene), polyglycidyl ethers of polysiloxane, and also contain heterocycles Examples of the epoxy resin include an epoxy resin in which an epoxy group is bonded to the oxazolidinone ring via a carbon atom, a diglycidyl ether of furan, a diglycidyl ether of dioxane, a diglycidyl ether of spiropi (m-dioxane), and a diglycidyl ether of dioxane. Examples include polyepoxy compounds obtained from imidazolines substituted with polyunsaturated alkenyl groups, triglycidyl isocyanurate, and the like.

Other “Production and Application of Epoxy Resins” (edited by Hiroshi Kakiuchi)
Conventionally known epoxy resins can be used, such as the various epoxy resins described in .

The compound (-1) having both an imidazoline ring and an amide bond used in the present invention is, for example, a polyamine having the ability to form an imidazoline ring and a fatty acid having three or more primary and/or secondary amino groups in one molecule. Alternatively, it can be obtained by reacting with a reactive derivative thereof by a conventionally known method.

Preferred polyamines used here include diethylenetriamine, triethylenetetramine, tetraethylenebentamine, pentaethylenehexamine,
Examples include hexaethyleneheptamine, heptaethylenemectamine, nonaethylenedecamine, di-1,2-propanetriamine, and other diamines such as aminoethylethanolamine and aminoethylpropanolamine are also within the scope of the present invention. can be used.

On the other hand, examples of fatty acids or their derivatives include butyric acid, valeric acid, caproic acid, hydrofuric acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid,
Saturated fatty acids with carbon atoms of 4 or more, such as pehenic acid, and their esters, citric acid, Linderic acid, lauroleic acid, tuzunic acid, fisetoleic acid, myristoleic acid, zomarinic acid, petroselic acid, oleic acid, elaidin acids, linoleic acid, 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 bulp manufacturing waste liquid and This ester, drying oil, semi-drying oil,
Alternatively, polymerized fatty acids such as dimer acid and trimer acid obtained by polymerizing these free fatty acids, and esters thereof can be mentioned. Here, the above-mentioned drying oil or semi-drying oil includes soybean oil, linseed oil, tung oil, eno oil, cottonseed oil, which contains highly unsaturated fatty acids such as linoleic acid, linolenic acid, etc.
Examples include sunflower oil, safflower oil, and dehydrated castor oil. Therefore, in the production of the above-mentioned compound (-1) containing an imidazoline ring and an amide bond, a fatty acid and/or its derivative and a polyamine are mixed in a conventional manner at 170 to 320° C., preferably at 250° C. under normal pressure. ~290
Obtained by heating to a temperature of °C.

This reaction may be carried out under reduced pressure in order to carry out the reaction at a low temperature while distilling off water produced by the condensation reaction. In addition, as the fatty acid and/or its derivative, it is preferable to use a polymerized fatty acid alone or a mixture of the polymerized fatty acid and a saturated fatty acid or an unsaturated fatty acid, and in the reaction with the above-mentioned polyamine, the reaction temperature and reaction time are adjusted appropriately. By doing so, a compound (-1) containing a desired imidazoline ring and amide bond can be obtained.

Preferred compounds (-1) containing an imidazoline ring and an amide bond obtained in this way contain an average of one or more imidazoline rings and an amide bond in one molecule, and an average of one or more imidazoline rings and an amide bond per minute. It contains primary and/or secondary amino groups. Further, as the epoxy compound (-2) used in the present invention, the compound exemplified above as the epoxy resin (4) and the monoepoxy compound include alkylene oxide such as propylene oxide, butyl glycidyl ether, propyl glycidyl ether,
Glycidyl ethers such as cetyl glycidyl ether, glycidyl ether of phenol or cresol, glycidyl ether of ether obtained by adding alkylene hydroxide to phenol, glycidyl ether of polypropylene glycol, and glycidyl methacrylate can be mentioned.

In the present invention, a compound (-1) having an imidazoline ring and an amide bond and an epoxy compound (-2) are reacted at 40 to 120°C, preferably 50 to 80°C, for several hours in such a proportion that active hydrogen atoms remain. The product (-3) used is obtained. The above compound (-1) and/or product (1-3) are used as epoxy resin curing agents, have excellent compatibility with engineered epoxy resin (4) and asphalt K), and are storage stable when mixed with asphalt. It also has good properties and forms a cured product with good adhesion and high strength.

Next, the asphalt used in the present invention includes natural asphalt, petroleum asphalt, (straight asphalt, plain asphalt).

The curable epoxy resin composition of the present invention contains a curing agent, that is, a compound (-1) and/or a product (-3), based on 100 parts by weight (hereinafter referred to as parts) of the epoxy resin (1).
It is desirable that the composition is made up of 10 to 150 parts, preferably 40 to 100 parts, and 50 to 500 parts, preferably 100 to 300 parts of asphalt.

The curable epoxy resin composition of the present invention also includes DBP.
, benzyl alcohol, furfuryl alcohol, phenol, alkyl phenol, mineral spirits, pine oil, naphtha, coal tar, and other plasticizers or diluents may also be added. The effects of the present invention are that the epoxy resin and asphalt have good compatibility, are stable, have good adhesive properties,
The object of the present invention is to provide a curable epoxy resin composition with excellent strength.

The present invention will be explained below with reference to production examples and examples.

In the examples, "parts" are parts by weight. Production example 1 284 parts of stearic acid and 235 parts of pentaethylenehexamine were added to a reactor equipped with a condenser and a depth meter, and 155 to 1
React at 70°C for 2 hours and then heat to 280°C under nitrogen gas flow.
A compound (-1) having an imidazoline ring, an amide bond, and a residual amino group after being reacted at 310°C for 2 hours and then dehydrated.
Obtained 480 copies.

This is called curing agent A. Production Example 2 In the same apparatus as Production Example 1, 50 parts of tall oil fatty acid, 200 parts of dimer acid (acid value 190), 48 parts of triethylenetetramine, and 10 parts of pentaethylenehexamine were mixed at 170 parts to 170 parts.
2 hours at 180℃, then 280~30℃ under nitrogen gas flow.
After reaction at 5° C. for 4 hours, the reaction mixture was dehydrated to obtain 367 parts of a compound (-1) having an imidazoline ring, an amide bond, and a residual amino group.

This is called curing agent B. Production Example 3 An epoxy compound having an epoxy equivalent of 320 which was obtained by adding propylene oxide to phenol in an equimolar ratio to 100 parts of the compound (-1) having an imidazoline ring and an amide bond obtained in Production Example 1, and then glycidyl etherification ( Add 20 parts of Asahi Denka Kogyo's ADEKA RESIN RD-501) to 80
The reaction was carried out at °C for 3 hours to obtain product (-3).

This is called curing agent C. Examples 1 to 4, Comparative Example 1 A curing agent, asphalt, and other components were mixed under heating at 90 to 100° C. in the formulation shown in Table 1, and the mixture was left in a room and cooled to observe stability.

This composition contains bisphenol A with an epoxy equivalent weight of 190.
The molded epoxy resin was applied to a mixed tin plate in the proportions shown in Table 1 in a chamber, and the film forming properties were observed. In addition, with the same composition,
Compressive strength and tensile shear strength were measured using a mild steel plate.

Claims (1)

[Claims] 1. As essential constituents, (I) an epoxy resin having more than one adjacent epoxy group per molecule on average, (II) a compound having both an imidazone ring and an amide bond (II-1) ) and/or the compound (
II-1) and a compound (II-2) having one or more epoxy groups in one molecule are reacted in a ratio such that the active hydrogen of compound (II-1) is in excess with respect to the epoxy group. Curable epoxy resin composition containing hardened product (II-3), (III) asphalt