JPS5948012B2 - Curable resin composition - Google Patents

Description

[Detailed description of the invention] The present invention relates to a curable resin composition.

It has been known for a long time to use an epoxy resin emulsion, an emulsion of a thermoplastic resin such as an acrylic resin, or a latex such as SBR in combination with an inorganic adhesive such as cement to strengthen strength and shorten the process. .

However, such conventional epoxy resin emulsions are unstable, hinder construction work, and have drawbacks in practicality. Furthermore, emulsions of thermoplastic resins such as acrylic resins or SBR latexes are not widely used because they cannot be modified to the extent expected due to insufficient reinforcement. The present inventors have discovered that in order to improve the above-mentioned drawbacks, it is sufficient to use a new water-dispersed curing agent having an imidazoline ring and an amide bond as an epoxy resin curing agent. Completed the invention.

An object of the present invention is to use a stable epoxy resin emulsion in combination with an inorganic adhesive such as cement to obtain a curable resin composition with excellent mechanical strength, drying properties, and workability.

The curable resin composition of the present invention contains, as essential components, an epoxy resin (I) having more than one adjacent epoxy group per molecule on average, and a compound having both an imidazoline ring and an amide bond (■- 1) An epoxy compound (■-2) which is liquid at room temperature and has one or more adjacent epoxy groups in one molecule on average, is added to the active hydrogen atom contained in the above compound (...-1), The above epoxy compound (■-
Contains an imidazoline ring-containing compound (■), water (110), and cement (material) obtained by reacting in excess of the epoxy group contained in 2).

The epoxy resin (I) used in the present invention has an average of 1 substituted or unsubstituted glycidyl ether group in the molecule (where Z is a hydrogen atom, a methyl group, or an ethyl group).
Epoxy resin (1-1) having more than one substituted or unsubstituted glycidyl ester group represented by the formula (where Z is a hydrogen atom, methyl group, or ethyl group) in its molecule on average (1-2), an epoxy resin having an average of more than one N-substituted or unsubstituted 1,2-epoxypropyl group in the molecule, represented by the formula (where Z is a hydrogen atom, a methyl group, or an ethyl group) (1-3) etc. are included.

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 ether (1-1-2) of an alcoholic polyhydroxyl compound derived by addition reaction with four alkylene oxides or polyglycidyl ether (1-1-3) of an aliphatic polyhydroxyl compound containing no nucleus ) etc.

However, polyglycidyl ether (1-1-1) is
For example, it can be obtained by reacting a polyhydric phenol (4) having at least one aromatic nucleus with an epihalohydrin (6) by a conventional method in the presence of a basic catalyst such as sodium hydroxide or a reaction amount of a basic compound. Epoxy resins containing polyglycidyl ethers such as polyglycidyl ethers as main reaction products or polyphenols having at least one aromatic nucleus (4
) and epihalohydrin (b) in the presence of a catalytic amount of a basic catalyst such as triethylamine by a conventional method, and a polyhydrin ether obtained by reacting with a basic compound such as sodium hydroxide. It is resin.

Similarly, polyglycidyl ether (-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 to 2.
A polyhydroxyl compound (C) derived by an addition reaction with four alkylene oxides or an aliphatic polyhydroxy compound C) that does not contain a nucleus and an epihalohydrin (b) are catalyzed by an acidic catalyst such as boron trifluoride. It is an epoxy resin containing as a main reaction product a polyglycidyl ether obtained by reacting a polyhalohydrin ether with a basic compound such as sodium hydroxide in the presence of a sufficient amount by a conventional method.

Here, the polyvalent phenol (4) having at least one aromatic nucleus includes a mononuclear polyvalent phenol (A-1) having one aromatic nucleus and a polynuclear polyphenol having two or more aromatic nuclei. phenol (A-2).

Examples of such mononuclear polyhydric phenols (A-1) include resorcinol, hydroquinone, 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 include a methyl group, n-propyl group, n-butyl group, n-hexyl group, n-
- an alkyl group such as an octyl group, preferably with up to 4 carbon atoms, or a halogen atom, i.e. a chlorine, bromine, iodine or fluorine atom, or a methoxy, methoxymethyl, ethoxy, ethoxyethyl group, Alkoxy groups such as n-ptoxy and amyloxy are preferably alkoxy groups 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 correspond to the number of hydrogen atoms in the aromatic ring (Ar) that can be substituted with a substituent. An integer having a value from zero to a maximum value, which can be the same or different values.

R1 is, for example, 11,0-O-, -S-, -SO-,
-SO2-, Ichiro) n- (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, 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, ω-(halogenated synchropentanenyl) alkylidene group Or a 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- and aryloxy-substituted alkylidene group or alkoxy- and aryloxy-substituted Alkylene group or alkoxy- and aryloxy-substituted cycloaliphatic group such as methoxymethylene group, ethoxymethylene group, ethoxyethylene group, 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) group, 1,4
-(2-fluorophenylene) group 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 an 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),
(wherein R2 is a hydrogen atom or a hydroxyl group is a hydrocarbon group which may be substituted with an epoxy group), or R1 is a divalent group such as It can also be a ring fused to one Ar group as in the case of the compound represented by ▲J, or R1 can be a polyethoxy group, polypropoxy group, polythioethoxy group, polyptoxy group, polyphenylethoxy group. or R1 can be a group containing a silicon atom, such as a polydimethylsiloxy group, a polydiphenylsiloxy group, a polymethylphenylsiloxy group; can be an aromatic ring, a tertiary amino group, an 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 are polynuclear divalent phenols.

Among such polynuclear divalent phenols, particularly preferred are)
1 general formula (A.2.卜1) (wherein, Y'
and Y1 have the same meanings as above, m and z have values of 0 to 4, R1 is preferably an alkylene group or alkylidene group having 1 to 3 carbon atoms, or a saturated group represented by the formula ρU, 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-bis(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)heptane, 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-phenylpropane or 4,4'-dihydroxybiphenyl, 4,4-dihydroxyoctachlorobiphenyl, 2,2'- dihydroxybiphenyl, dihydroxybiphenyl or bis(4-hydroxyphenyl) sulfone such as 2,4'-dihydroxybiphenyl, 2,4'-dihydroxydiphenyl sulfone, chloro-2,4-dihydroxydiphenyl sulfone, Di(hydroxyphenyl) sulfone or bis(4-hydroxyphenyl) ether such as 5-chloro-4,4'-dihydroxydiphenyl sulfone, 3'-chloro-4,4'-dihydroxydiphenyl sulfone, 4,3'-(or 4,2L or 2,2'-dihydroxydiphenyl)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) ether,
Bis(4-hydroxy-3-fluorophenyl) ether, bis(4-hydroxy-3-promphenyl) ether, bis(4-hydroxynaphthynolyether, bis(4-hydroxy-3-chlornaphthyl) ether, Bis(2-hydroxybiphenyl)ether, 4,4'-
Di(hydroxyphenyl) ethers such as dihydroxy-2,6-dimethoxydiphenyl ether, 4,4'-dihydroxy-2,5-diethoxydiphenyl ether, and 1,1-bis(4- hydroxyphenyl)
1-2-phenylethane, 1,3,3-trimethyl-1-
(4-hydroxyphenyl)-6-hydroxyindan, 2,4-bis(p-hydroxyphenyl)-4-
Methylpentane 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 o 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 pentanediallyl, condensation reaction product of resorcinol and acetone, xylene-phenol-formalin initial condensation products), condensation reaction products of phenols and polychloromethylated aromatic compounds (eg, condensation reaction products of phenols and bischloromethylxylene), and the like.

Therefore, the term "polyhydroxyl compound (self)" herein refers to the above-mentioned polyhydric phenol having at least one aromatic nucleus (
-ROH (where R is alkylene group derived from alkylene oxide) or (and) -(RO)NH(
Here, R is an alkylene group derived from alkylene oxide, and one polyoxyalkylene 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 ^ to the alkylene oxide is 1:1 (mol limole) or more, but preferably the ratio of the alkylene oxide to the 0H group of the polyhydric phenol 4 is 1:1 to 10, preferably is 1:1 to 3 (equivalent: equivalent). Examples of alkylene oxide include ethylene oxide,
There are propylene oxide, butylene oxide, etc., but those which form a side chain when reacting with the polyhydric phenol (support) to form an ether bond are particularly preferred. butylene oxide, 2,3-butylene oxide, 1,
3-Butylene oxide is preferred, especially propylene oxide.

Among such polyhydroxyl compounds, a particularly preferable group has the general formula (wherein Y', Yl, m,
z and R1 are the same as those in A-2-1-1, R is an alkylene group having 2 to 4 carbon atoms, nl and N
2 is a value 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 nl and N2 are values of 1 to 3). It is.

Other polyhydroxyl compounds containing nuclei include alicyclic polyols obtained by hydrogenating aromatic nuclei of polyhydroxyl compounds. Examples of the aliphatic polyhydroxyl compound O that does not contain a nucleus include polyhydric alcohols such as ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, dibutylene glycol, glycerin, and pentaerythritol; Polyhydroxyl compounds such as polyhydric alcohols or other active hydrogen-containing compounds (for example, compounds with groups such as amino groups, carboxyl groups, thiohydroxyl groups, etc.) and alkylene oxides, polyether polyols, etc. Can be mentioned. In addition, the epihalohydrin (b) herein has the general formula (where Z is a hydrogen atom, a methyl group, an ethyl group, and X' is a halogen atom).
This epihalohydrin (b
) Examples include epichlorohydrin, epibromohydrin, 1,2-epoxy-2-methyl-3-chloropropane, 1,2-epoxy-2-ethyl-3-chloropropane, and the like.

Examples of acidic catalysts that promote the reaction between the epihalohydrin (b) and the polyhydroxyl compound 8 or the polyhydroxyl compound (C) include Lewis acids such as boron trifluoride, stannic chloride, zinc chloride, and ferric chloride; Derivatives exhibiting these activities (eg, boron trifluoride monoether complex compound) or mixtures thereof can be used.

Similarly, epihalohydrin (b) and polyhydric phenol (4
), 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, can be used to generate glycidyl ethers simultaneously with such reactions, or to react with halohydrin ethers formed as a result of the reactions. Examples of basic compounds that can be ring-closed by dehydrohalogenated carbon reaction to produce glycidyl ether include alkali metal hydroxides (e.g., sodium hydroxide), alkali metal salts of aluminate (e.g., sodium aluminate), etc. is conveniently used.

Of course, these catalysts and basic compounds can be used as they are or as solutions in appropriate inorganic and/or organic solvents.

In addition, the epoxy resin (1-2) having on average one or more substituted or unsubstituted glycidyl ester groups in its molecule may include aliphatic polycarboxylic acids or aromatic polycarboxylic acids (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,
In addition to succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dimer fatty acids, trimellitic acid, trimesic acid, pyromellitic acid, cyclopentanetetracarboxylic acid, these halogen-substituted compounds, There are polyglycidyl esters, etc., which may also include terminal carboxyl polyester oligomers obtained from polyhydric carboxylic acids and polyhydric alcohols.
For example, epoxy resins such as those obtained by polymerizing glycidyl methacrylate synthesized from epihalohydrin (b) represented by the above general formula and methacrylic acid are also included. Examples of epoxy resins (1-3) having more than one N-substituted or unsubstituted 1,2-epoxypropyl group in the molecule include aromatic amines (e.g. aniline or alkyl substituents in the nucleus). Epoxy resin obtained from the epihalohydrin (b) represented by the general formula above, an initial condensate of an aromatic amine and an aldehyde (for example, an aniline-formaldehyde initial condensate, an aniline-phenol-formaldehyde initial condensate) ) and epihalohydrin (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 dioxide, 1-(1-methyl-1,2-epoxyethyl)-3,4-epoxy-4-methylcyclohexane, 3
, 4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, bis(
3,4-epoxy-6-methylcyclohexylmethyl) adipate, synchropentane edge oxide, dipentene dioxide, tetrahydroindene dioxide, or these rings were previously shown as R1 in general formula (A-2-1) Compounds bonded with groups such as Araldite CY-175 (Ciba product name)
), epoxidized products of conjugated diene polymers (e.g., epoxidized polybutadiene, epoxidized styrene-butadiene copolymers, epoxidized acrylonitrile-styrene copolymers), epoxidized products of polymers containing unsaturated bonds ( For example, epoxidized polypropylene, epoxidized polyisobutene), polyglycidyl ether of polysiloxane, and epoxy resins containing heterocycles include epoxy resins in which an epoxy group is bonded to the oxazolidinone ring via a carbon atom, diglycidyl ether of furan. compound, diglycidyl ether of dioxane, diglycidyl ether of spirobi(m-dioxane),
Examples include polyepoxy compounds obtained from imidazolines substituted with a polyunsaturated alkenyl group at the 2-position, triglycidyl isocyanurate, and the like.

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. 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 having three or more primary and/or secondary amino groups in one molecule. It can be obtained by reacting a fatty acid or a reactive derivative thereof by a conventionally known method.

Preferred polyamines used here include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine,
Examples include hexaethyleneheptamine, heptaethyleneoctamine, nonaethylenedecamine, di-1,2-propanetriamine, and other diamines such as aminoethylethanolamine and aminoethylpropanolamine are also included 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, chifurylic acid, chipurinic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid,
Saturated fatty acids with a carbon number of 4 or more, such as behenic acid, and their esters, tuccinic acid, lindic acid, lauroleic acid, tussic acid, physetoleic acid, myristoleic acid, zomarinic acid, petroselic acid, oleic acid, elaidic acid, 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 valve manufacturing waste liquid and their esters, drying Examples include 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 linolenic acid. Examples include oil. Therefore, in the production of the compound (-1) containing an imidazoline ring and an amide bond, fatty acids and/or
Alternatively, it can be obtained by heating a derivative thereof and a polyamine in a conventional manner, for example, at a temperature of 170 to 320°C, preferably 250 to 290°C, under normal pressure.

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. As the fatty acid and/or its derivative, it is preferable to use polymerized fatty acid alone or a mixture of polymerized fatty acid and saturated fatty acid or unsaturated fatty acid. In the reaction with the above-mentioned polyamine, the reaction temperature and reaction time should be adjusted appropriately. Compound (-1) containing a desired imidazoline ring and amide bond can be obtained by the following steps.

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 in one molecule. It contains primary and/or secondary amino groups. Further, as the epoxy compound (12) used in the present invention, among the compounds exemplified above as the epoxy resin (I), those which are liquid at room temperature, and as monoepoxy compounds, alkylene oxides such as propylene oxide, butyl glycidyl ether , propyl glycidyl ether, cetyl glycidyl ether,
Examples include glycidyl ether of phenol or cresol, glycidyl ether of ether obtained by adding alkylene oxide to phenol, glycidyl ether of polypropylene glycol, and glycidyl ester such as glycidyl methacrylate.

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 imidazoline ring-containing compound () used is obtained.

The mixing ratio of the imidazoline ring-containing compound () and the epoxy resin (1) is from 120 to 120 parts by weight per 100 parts by weight of (1).
It is permissible within the range of 300 parts by weight, but preferably 40 to 10 parts by weight.
It is 0 parts by weight.

This range depends on the equivalence relationship during curing of the epoxy resin,
It is determined by the balance with the affinity for water, and conversely, it is better to adjust the number of remaining active hydrogen atoms in the imidazoline ring-containing compound () so that a good curing state can be obtained at this ratio. In addition, the cements (5) used in the present invention refer to various cements such as plaster type 1 such as lime and gypsum, portland cement, slag cement, alumina cement, and mixed cement, and preferred ones include calcined stone and various cements. Among others, Portland cement is used.

The composition of the present invention comprises 100 parts by weight of epoxy resin (1) (
(hereinafter referred to as part), the imidazoline ring-containing compound (hereinafter referred to as part)
)20-300 parts, preferably 40-100 parts, water (1
1) 10-3000 parts, preferably 100-1000 parts, cement (IV) 10-5000 parts, preferably 5
00 to 2000 parts.

The epoxy resin (1) and the imidazoline ring-containing compound () of the present invention become a stable emulsified state only in the presence of water. There is no need to be afraid of sexuality.

In addition, these organic components are economical because they can sufficiently exhibit their properties in a relatively small amount compared to cement.

Furthermore, if necessary, a solvent such as mineral spirits, ethylene glycol monomethyl ether, or ethylene glycol monomethyl ether acetate may be added in addition to water.

Furthermore, if necessary, diluents such as DBP, DOP, furfuryl alcohol, tetrahydrofurfuryl alcohol, and benzyl alcohol, other epoxy resin curing agents, titanium oxide, talc, silica powder, pigments, calcium carbonate, mica, and clay may be used. Fillers such as those described above may also be used in combination. In addition, plasticizers such as white tar, coal tar, xylene resin, and biphenyl may be added. The effects of the present invention are that it provides a stable epoxy resin emulsion that can be used in combination with cements, and further improves mechanical strength, caking properties, drying properties, and
Another object of the present invention is to provide a cement-containing curable resin composition with excellent workability.

The present invention will be explained below with reference to production examples and examples, but the present invention is not limited to these production examples and examples.

In addition, "part" in an Example shows a weight part. Production Example 1 284 parts of stearic acid and 235 parts of pentaethylenehexamine were added to a reactor equipped with a condenser and a thermometer.
React at 70°C for 2 hours and then heat to 280°C under nitrogen gas flow.
After reacting at 310°C for 2 hours and then dehydrating, Compound 3 having an imidazoline ring, an amide bond, and a residual amino group was obtained at 48°C.
I got 0 copies.

Production Example 2 Tall oil fatty acid 50% was prepared using the same equipment as Production Example 1.
1 part, 200 parts of dimer acid (acid value 190), 48 parts of triethylenetetramine, and 10 parts of pentaethylenehexamine at 170 to 180°C for 2 hours, and further under a nitrogen gas stream for 2 hours.
After reaction at 80 to 305°C for 4 hours, dehydration was performed to obtain compound 8 having an imidazoline ring, an amide bond, and a residual amino group.
I got 7 copies.

Production Example 3 Compound (4) 10 having an imidazoline ring obtained in Production Example 1
To 0 parts, 20 parts of an epoxy compound having an epoxy equivalent of 320 (ADEKA RIN ED-501 manufactured by Asahi Denka Kogyo), which was obtained by adding propylene oxide to phenol in an equimolar ratio and then glycidyl etherification, were added and reacted at 80°C for 3 hours. to obtain curing agent a].

Production Example 4 Compound 03)10 containing an imidazoline ring obtained in Production Example 2
0 parts and diglycidyl ether of polyether prepared by adding propylene oxide to 2,2-bis(4-hydroxyphenyl)propane (Adeka Resin EP- manufactured by Asahi Denka Kogyo Co., Ltd.)
4,000, epoxy equivalent: 320) was added and reacted at 80°C for 3 hours to obtain a curing agent (button).

Examples 1 to 4 Curable resin compositions were produced according to the proportions shown in Table 1 below, and tested for strength, drying properties, etc.

Note Al5Om7! L×25m7! L x 25 mm test piece b (1) 15 x 30 mm test piece Comparative Examples 1 to 3 A curable resin composition was manufactured with the formulation shown in the following Table 2, and tests were conducted on strength, drying properties, etc. Ta.

Note a However, in Comparative Example 3, the Bl5Omm
25mm x 25mm test piece c (1) 15mm x 30
dragon test piece

Claims (1)

[Claims] 1 Epoxy resin (I) having on average more than one adjacent epoxy group in one molecule as an essential component 10
0 parts by weight, and an epoxy compound (II-2) which is liquid at room temperature and has one or more adjacent epoxy groups in one molecule on average, is added to the compound (II-1) having both an imidazoline ring and an amide bond. An imidazoline ring-containing compound obtained by reacting the active hydrogen atoms contained in the above compound (II-1) in excess of the epoxy groups contained in the above epoxy compound (II-2). (II) 20-30
1. A curable resin composition comprising: 0 parts by weight, 10 to 3,000 parts by weight of water (III), and 10 to 5,000 parts by weight of cement (IV).