JPH04325521A - Curable epoxy resin composition - Google Patents

Abstract

PURPOSE:To provide the title composition which is excellent in film-forming properties and can be cured even under high-humidity and low- or high- temperature conditions without forming any amine brush to give a cured film excellent in surface gloss, initial hardness and resistance to water whitening. CONSTITUTION:A curable epoxy resin composition comprising an epoxy resin having more than one vicinal epoxy group on the average per molecule, a polyamine having at least one N-bonded active hydrogen atom, and a reaction product obtained by reacting 1mol of a phenol having at least one unsubstituted reactive position in the aromatic nucleus with at least 1mol of a carbonyl compound having at least one carbonyl group in the molecule and at least one mol of an alkyltrimethylenediamine represented by the general formula: R-NH- CH2CH2CH2-NH2 (wherein R is 8-22C alkyl).

Description

[Detailed description of the invention]

0001

FIELD OF THE INVENTION This invention relates to curable epoxy resin compositions. More specifically, the present invention cures even in film form without producing amine brushing even under high humidity, low temperature and high temperature, and the surface gloss of the cured coating film,
The present invention relates to a curable epoxy resin composition with excellent rising hardness and water whitening resistance.

0002

[Prior Art and Problems to be Solved by the Invention] Epoxy resins are used for paints, civil engineering and construction, etc., and have excellent surface gloss without surface whitening, such as amine brushes, even under high humidity, low and high temperatures. is required. There are various types of epoxy resin curing agents that are conventionally used.
Examples include polyamines, polyamides, and various modified versions thereof. However, these curing agents do not necessarily give a satisfactory cured product under the above-mentioned severe conditions. For example, under conditions of high humidity, polyamides exhibit a whitening phenomenon on the surface due to amine brushing, and also have poor rising hardness, making it impossible to obtain a satisfactory coating surface. Furthermore, under high humidity and low temperatures, polyamines may cause whitening or sweatering on the surface due to amine brushing, or may cause repellency, making it impossible to obtain a satisfactory coating surface. In addition, curing agents using Mannich bases based on phenols/polyamines/carbonyl compounds as disclosed in Japanese Patent Publication No. 49-48480, and Mannich bases based on polyethylene polyamines or alicyclic diamines/phenols/aldehydes as disclosed in Japanese Patent Publication No. 52-20460. cures with a good surface condition to some extent, but whitening occurs when a water whitening test is carried out after a short period of curing, so it is not perfect.

0003

[Means for Solving the Problems] As a result of intensive research to improve the conventional drawbacks, the present inventors have found that the film-forming property is excellent.
We have discovered a curable epoxy resin composition that cures without producing amine brushing even under high humidity, low temperature, and high temperature conditions, and has excellent surface gloss, rising hardness, and water whitening resistance of the cured coating film, and has achieved the present invention. completed.

That is, the curable epoxy resin composition of the present invention contains (i) an epoxy resin having an average of more than one adjacent epoxy group in the molecule; (ii)
Polyamines having one or more active hydrogen atoms bonded to a nitrogen atom, and (iii) phenols having at least one reactive position not substituted with an aromatic nucleus (iii-1) per mole of carbonyl Carbonyl compound having at least one group in the molecule (iii-2
) 1 mol or more and the general formula R-NH-CH2-CH2-CH2-NH2 (
It is characterized by containing a reaction product obtained by reacting with 1 mol or more of alkyltrimethylenediamine (iii-3) represented by the formula (R is an alkyl group having 8 to 22 carbon atoms).

The epoxy resin (i) having an average of more than one adjacent epoxy group in the molecule includes, for example, an epoxy resin having an average of more than one 1,2-epoxy group in the molecule, preferably Epoxy resin having an average of more than one substituted or unsubstituted glycidyl ether group in the molecule, an epoxy resin having an average of more than one substituted or unsubstituted glycidyl ester group in the molecule, N-substituted or unsubstituted 1 , 2-epoxypropyl groups on average more than one in the molecule, epoxidized polyunsaturated compounds, and other conventionally known epoxy resins containing adjacent epoxy groups.

In such a molecule there is on average more than one 1,
A preferred example of the epoxy resin having a 2-epoxy group is the formula

[0007]

[Chemical formula 1]

(where Z is a hydrogen atom, a methyl group, or an ethyl group) Epoxy resin (i
-1), formula

[0009]

[Case 2]

(where Z is a hydrogen atom, a methyl group, or an ethyl group) Epoxy resin (i
-2), formula

[0011]

[Chemical formula 3]

(where Z is a hydrogen atom, a methyl group, or an ethyl group) An epoxy resin (i-3 ) etc. are included.

Epoxy resin having more than one substituted or unsubstituted glycidyl ether group in the molecule (i-1
) are epoxy resins obtained by glycidyl etherification of phenolic hydroxyl groups and epoxy resins obtained by glycidyl etherification of alcoholic hydroxyl groups, and preferred examples of such epoxy resins (i-1) include one or polyglycidyl ether of polyhydric phenol having two or more aromatic nuclei (i-1-1)
and polyglycidyl ether (i-1-2) of an alcoholic polyhydroxyl compound derived by the addition reaction of a polyhydric phenol having one or more aromatic nuclei and an alkylene oxide having 2 to 4 carbon atoms. Alternatively, polyglycidyl ether (i-1-3) of an aliphatic polyhydroxyl compound containing no nucleus may be mentioned.

[0014] Polyglycidyl ether (i-1
-1) means, for example, that polyhydric phenol (A) having at least one aromatic nucleus and epihalohydrin (b) are mixed in a conventional manner in the presence of a reaction amount of a basic catalyst or basic compound such as sodium hydroxide. An epoxy resin containing a polyglycidyl ether as the main reaction product, such as obtained by reacting a polyhydric phenol (A) having at least one aromatic nucleus, and an epihalohydrin (b) in a catalytic amount of a basic catalyst such as triethylamine. It is an epoxy resin obtained by reacting a polyhydrin ether obtained by a conventional method in the presence of a basic compound such as sodium hydroxide.

Similar polyglycidyl ether (i-1-2
) or polyglycidyl ether (i-1-3),
For example, a polyhydroxyl compound (B) derived by an addition reaction between a polyhydric phenol having at least one aromatic nucleus and an alkylene oxide having 2 to 4 carbon atoms or an aliphatic polyhydroxy compound (C ) and epihalohydrin (b) by a conventional method in the presence of an acidic catalyst amount such as boron trifluoride, and a polyhalohydrin ether obtained by reacting a basic compound such as sodium hydroxide. It is an epoxy resin containing polyglycidyl ether as the main reaction product.

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

Examples of such mononuclear polyhydric phenol (A-1) include resorcinol, hydroquinone, pyrocatechol, phloroglucinol, 1,5-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,6-dihydroxy Examples include naphthalene.

Further, as an example of polynuclear polyhydric phenol (A-2), the general formula

[0019]

[C4]

[0020] In the formula, Ar is an aromatic divalent hydrocarbon such as naphthylene and phenylene, with phenylene being preferred for the purposes of the present invention. Y' and Y1 may be the same or different and are alkyl groups, preferably having up to 4 carbon atoms, such as methyl, n-propyl, n-butyl, n-hexyl, n-octyl. an alkyl group or a halogen atom, i.e., a chlorine atom, a bromine atom, an iodine atom or a fluorine atom, or an alkoxy group such as a methoxy, methoxymethyl, ethoxy, ethoxyethyl, n-butoxy, amyloxy group, preferably up to 4 It is an alkoxy group with 5 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 aromatic rings (Ar
) is an integer having a value from 0 (zero) to a maximum value corresponding to the number of hydrogen atoms, and can be the same or different values. For example, R1 is

[0021]

[C5]

(n is an integer of 2 to 6) 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, ω-(halogenated dicyclopentadienyl) 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 group, or a halogenated cycloaliphatic group,
or alkoxy- and aryloxy-substituted alkylidene groups, or alkoxy- and aryloxy-substituted alkylene groups, or alkoxy- and aryloxy-substituted cycloaliphatic groups such as methoxymethylene groups, ethoxymethylene groups, ethoxy Ethylene 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-phenoxytrimethylene group,
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) groups,
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, formula

[0023]

[C6]

(wherein R is a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms), a group represented by the formula

00
25]

[Chemical 7]

(wherein R4 is a hydrogen atom or a hydrocarbon group optionally substituted with a hydroxyl group or an epoxy group), or R1 is a divalent group such as

[0027]

[Chemical formula 8]

It can also be a ring fused to one of the Ar groups as in the case of the compound represented by the formula, or R1 can be a polyethoxy group, a polypropoxy group, a polythioethoxy group, a polybutoxy group, a polybutoxy group, etc. It can also be a polyalkoxy group, such as a phenylethoxy group, or R1 can be, for example, a polydimethylsiloxy group, a polydiphenylsiloxy group,
It can be a group containing a silicon atom, such as a polymethylphenylsiloxy group, or R1 is separated by an aromatic ring, a tertiary amino ether bond, a carbonyl group, or a sulfur-containing bond such as sulfur or sulfoxide. It can be two or more alkylene or alkylidene groups. ] There is a polynuclear dihydric phenol represented by

Particularly preferred polynuclear dihydric phenols have the general formula

[0030]

[Chemical formula 9]

(wherein Y' and Y1 have the same meanings as above, m and z have values of 0 to 4, and R1 is preferably an alkylene group or alkylidene group having 1 to 3 carbon atoms, or formula

[0032]

[Chemical formula 10]

It is a polynuclear dihydric phenol represented by a saturated group represented by: 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-
Chlorphenyl)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)cyclohexyl Methane, 1,2-bis(4-hydroxyphenyl)-1,2-bis(phenyl)propane, 2,
bis(hydroxyphenyl) alkanes, such as 2-bis(4-hydroxyphenyl)-1-phenylpropane;
or 4,4'-dihydroxybiphenyl, 4,4'-
Dihydroxybiphenyls such as dihydroxyoctachlorobiphenyl, 2,2'-dihydroxybiphenyl, 2,4'-dihydroxybiphenyl, or bis(4-hydroxyphenyl)sulfone, 2,4'-dihydroxydiphenylsulfone, chlor-2,4 - di(hydroxyphenyl) sulfones such as dihydroxydiphenyl sulfone, 5-chloro-4,4'-dihydroxydiphenyl sulfone, 3'-chloro-4,4'-dihydroxydiphenyl sulfone, or bis(4-hydroxyphenyl) ether , 4,3'-(or 4,2'- 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-bromphenyl) 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
-Di(hydroxyphenyl) ethers such as -diethoxydiphenyl ether, and also 1,1-bis(4-hydroxyphenyl)-2-phenylethane,
1,3,3-trimethyl-1-(4-hydroxyphenyl)-6-hydroxyindan, 2,4-bis-(
p-hydroxyphenyl)-4-methylpentane is also suitable.

Another group of preferred polynuclear dihydric phenols has the general formula

[0036]

[Chemical formula 11]

(Here, R3 is a methyl or ethyl group, R2
is an alkylidene group or other alkylene group having 1 to 9 carbon atoms, p is 0 to 4), for example, 1
, 4-bis(4-hydroxybenzyl)benzene, 1,
4-bis(4-hydroxybenzyl) tetramethylbenzene, 1,4-bis(4-hydroxybenzyl)
Examples include tetraethylbenzene, 1,4-bis(p-hydroxycumyl)benzene, and 1,3-bis(p-hydroxycumyl)benzene.

Other polynuclear polyhydric phenols (A-2) include, for example, initial condensates of 1,1,2,2-tetrakis(4-hydroxyphenyl)ethanephenols and carbonyl compounds ( Examples: Phenol resin initial condensate, condensation reaction product of phenol and acrolein, phenol and glyoxal condensation reaction product, condensation reaction product of phenol and pentanediallyl, condensation reaction product of resorcinol and acetone, xylene-
(phenol-formalin initial condensate), condensation products of phenols and polychloromethylated aromatic compounds (e.g. condensation products of phenol and bischloromethylxylene)
etc. can be mentioned.

[0039] Here, a polyhydroxyl compound (
B) is an ether obtained by reacting the above polyhydric phenol (A) having at least one aromatic nucleus with an alkylene oxide in the presence of a catalyst that promotes the reaction between an OH group and an epoxy group. -ROH (where R is an alkylene group derived from an alkylene oxide) bound to the phenol residue by a bond or (and) -(RO)nH (where R is an alkylene group derived from an alkylene oxide) The polyoxyalkylene chain is a compound having an atomic group (n is 2 or an integer of 2 or more indicating the number of polymerized oxyalkylene groups), which may contain different alkylene groups. In this case, the ratio of the polyhydric phenol (A) to the alkylene oxide is 1:1 (mol: mol) or more, but preferably the ratio of the alkylene oxide to the OH group of the polyhydric phenol (A) is 1:1 (mol: mol) or more. :1-10, preferably 1:1-3(
Equivalent weight: equivalent weight).

Examples of the alkylene oxide 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. , such as propylene oxide, 1,2-butylene oxide, 2,
3-Butylene oxide is preferred, especially propylene oxide.

A particularly preferred group of polyhydroxyl compounds (B) have the general formula

[0042]

[Chemical formula 12]

(In the formula, Y', Y1, m, z and R1 are the same as those in the above formula (A-2-1-1), R is an alkylene group having 2 to 4 carbon atoms, n1 and n2 is a value of 1 to 3).

Furthermore, another preferred group of such polyhydroxyl compounds has the general formula

004
5]

[Chemical formula 13]

(wherein R2, R3 and p are the above (A
-2-1-2) is the same as that of formula, R has 2 carbon atoms
~4 alkylene groups, n1 and n2 having values of 1-3. ) is a polyhydroxyl compound represented by

Other polyhydroxyl compounds containing a nucleus (
B) includes aliphatic polyols obtained by hydrogenating the aromatic nucleus of polyhydric phenol (A).

Examples of the aliphatic polyhydroxy compound (C) which does not contain a nucleus include polyhydric compounds such as ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, dibutylene glycol, glycerin, and pentaerythritol. Polyhydric polyhydroxy compounds, polyether polyols, etc. in which alkylene oxide is added to alcohols and these polyhydric alcohols or other active hydrogen-containing compounds (for example, compounds with groups such as amino groups, carboxyl groups, and thiohydroxyl groups). Examples include polyhydroxyl compounds.

[0049] Also, the epihalohydrin (b)
is the general formula

[0050]

[Chemical formula 14]

(Here, Z is a hydrogen atom, a methyl group, an ethyl group, and X' is a halogen atom.) Examples of such epihalohydrin (b) include epichlorohydrin and epibromohydrin. , 1,2
-Epoxy-2-methyl-3-chloropropane, 1,
Examples include 2-epoxy-2-ethyl-3-chloropropane.

[0052] The epihalohydrin (b) and the polyhydroxyl compound (B) or the polyhydroxyl compound (C
) as acidic catalysts that promote the reaction with boron trifluoride,
Lewis acids such as stannic chloride, zinc chloride, and ferric chloride, derivatives exhibiting these activities (eg, boron trifluoride-ether complex compounds), or mixtures thereof can be used.

[0053] Similarly, as basic catalysts that promote the reaction between epihalohydrin (b) and polyhydric phenol (A), alkali metal hydroxides (eg, sodium hydroxide),
Alkali metal alcoholates (e.g. sodium ethylate), tertiary amine compounds (e.g. triethylamine, triethanolamine), quaternary ammoniums (e.g. tetramethylammonium bromide), or mixtures thereof can be used, but Examples of basic compounds that generate glycidyl ether simultaneously with such a reaction, or ring-close the halohydrin ether generated as a result of the reaction by dehydrohalogenation reaction, include alkali metal hydroxides (e.g. (sodium hydroxide), alkali metal aluminates (eg, sodium aluminate), etc. are conveniently used.

It goes without saying that these catalysts and basic compounds can be used as they are or as solutions in appropriate inorganic and/or organic solvents.

[0055] Epoxy resins (i-
2) includes 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, Phthalic acid, methylendomethylenetetrahydrophthalic acid, maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dimer fatty acid, trimellitic acid, trimesin In addition to halogen-substituted compounds of these acids, pyromellitic acid, cyclopentanetetracarboxylic acid, and polyhydric alcohols, there are also polyglycidyl esters of carboxylic acid, pyromellitic acid, cyclopentane tetracarboxylic acid, and halogen-substituted compounds thereof, as well as terminal carboxyl polyester oligomers obtained from these 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.

[0056] Also, substituted or unsubstituted N-substituted 1,2-
Examples of epoxy resins (i-3) having more than one epoxypropyl group in the molecule include aromatic amines (
For example, epoxy resins obtained from aniline or aniline having an alkyl substituent in the nucleus) and epihalohydrin (b) represented by the above general formula, initial condensates of aromatic amines and aldehydes (for example, aniline-formaldehyde initial condensates, aniline - phenol-formaldehyde initial condensate) and epihalohydrin (b).

Other epoxy resins include epoxidized oils (for example, 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. vinyl cyclohexene 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, dicyclopentaene dioxide, dipentene dioxide, tetrahydroindene dioxide, or these rings are first formed by the general formula (A- Compounds bonded with groups such as those shown as R1 in 2-1), and other Araldite OY-1
75 (Ciba product, trade name)], epoxidized products of conjugated diene polymers (e.g., epoxidized polybutadiene, epoxidized polypentadiene, epoxidized styrene-butadiene copolymer, epoxidized acrylonitrile-styrene copolymer) epoxidized polymers containing unsaturated bonds (e.g. epoxidized polypropylene,
Epoxides of polyisobutene), polyglycidyl ethers of polysiloxane, epoxy resins containing heterocycles include epoxy resins in which an epoxy group is bonded to the oxazolidinone ring via a carbon atom, diglycidyl ethers of furan, and dioxane diglycidyl ethers. Examples thereof include glycidyl etherified products, diglycidyl etherified products of spirobi(m-dioxane), polyepoxy compounds obtained from imidazolines substituted with a polyunsaturated alkenyl group at the 2-position, and triglycidyl isocyanurate. 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.

Polyamines (ii) used in the present invention
is an aromatic polyamine, for example, the general formula

005
9]

[Chemical formula 15]

(However, in the formula, A is a mononuclear or dinuclear aromatic compound residue, Y is a nuclear-substituted alkyl group having 1 to 4 carbon atoms, an alkoxy group, a hydroxyl group, or a halogen atom, and q is 1 or 2; A branched or straight-chain alkylene group, oxyalkylene group, or a divalent aliphatic compound residue having an ether oxygen atom having 1 to 3 atoms; n is a number of 0 or 1 or more) An aromatic polyamine (ii-1) having at least two aromatic nuclei is mentioned.

Aromatic polyamine represented by the above general formula (
As a group of compounds of ii-1), the general formula

0062
]

[Chemical formula 16]

(Here, Y, q, r are X1 as mentioned above.
is a methylene group or an oxymethylene group, and n is a number of 0 or 1 or more, preferably 1 or more.

In the above general formula,

[0065]

[Chemical formula 17]

The mononuclear aromatic amine corresponding to the bond is:
general formula

[0067]

[Chemical formula 18]

(However, in the formula, Y is the number of carbon atoms in the nuclear substitution: 1
~4 alkyl groups, alkoxy groups, hydroxyl groups, or halogen atoms, q is 1 or 2, and r is 0 or a number of 4 or less corresponding to the number of hydrogen atoms in the aromatic nucleus that can be substituted by a substituent. ) is a compound represented by

The polycyclic aromatic polyamine represented by the above general formula can be obtained by reacting a mononuclear aromatic amine with an aldehyde or a reactive derivative of an aldehyde in a conventional manner to obtain at least 2 moles of a mononuclear aromatic amine. It can be obtained by bonding with a methylene group or an oxymethylene group.

The mononuclear aromatic amine here has at least one reactive position that is not substituted with an aromatic nucleus, and preferred examples include aniline substituted with a polynuclear alkyl group.

As the nuclear alkyl-substituted aniline,
Examples include toluidine, ethylaniline, xylidine, and the like.

In addition, as another group of compounds of the aromatic polyamine (ii-1) represented by the above general formula,

[0073]

[Chemical formula 19]

(However, in the formula, Ar' is a dinuclear aromatic compound residue, Y and r are the same as in the above general formula, X1 is a methylene group or oxymethylene group, and n is a number of 0 or 1 or more, preferably is 0).

In the above general formula,

[0076]

[C20]

The dinuclear aromatic diamine corresponding to the bond has the general formula (Y)r-Ar'-(NH2)2 (wherein Ar' is a dinuclear aromatic compound residue, Y
and r are the same as in the above general formula).

Among the binuclear aromatic diamines represented by the above general formula, a preferable group is represented by the general formula

[0079]

[C21]

(However, in the formula, X2 is a branched or linear alkylene group having 1 to 3 carbon atoms, -O-, -SO2-
, -CO-, and Y1 is a nuclear substituted carbon atom number of 1 to 4
is an alkyl group or a methoxy group, m is 0 or 1, u
is 0 or 1).

Among the binuclear aromatic diamines represented by the above general formula, a preferable group is

[0082]

[C22]

(However, in the formula, X2 and u are the same as in the general formula above.) Examples of such diamines include benzidine, 4,4'-diaminodiphenylmethane, 2,2-bis(4 -aminophenyl)
Propane, 4,4'-diaminodiphenyl ether, 4
, 4'-diaminodiphenylsulfone, 4,4'-diaminobenzophenone, and the like.

Other examples of aromatic diamines represented by the above general formula include 2,2'-dimethyl-4,4'
-diaminodiphenylmethane, 2,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4-diaminobiphenyl, and the like.

The aromatic polyamine represented by the above general formula is prepared by reacting a dinuclear aromatic diamine with an aldehyde or a reactive derivative of an aldehyde in a conventional manner.
It can be obtained by bonding a nuclear aromatic diamine with a methylene group or an oxymethylene group.

Examples of aldehydes and reactive derivatives of aldehydes include aliphatic lower aldehydes such as formaldehyde, paraformaldehyde, acetaldehyde, and chloral, with formaldehyde or its reactive derivatives being particularly preferred.

For example, formaldehyde can be used in the form of an aqueous solution or in the form of a solution in an organic solvent such as methanol.

[0088] Other cycloaliphatic polyamines include 1,4-cyclohexanediamine,
4,4'-methylenebiscyclohexylamine, 4,4
'-Isopropylidene biscyclohexylamine, isophorone diamine, etc.

Other aromatic polyamines of the group include ortho-xylylene diamine, meta-xylylene diamine, para-xylylene diamine, and the like.

Other polyamines containing other ring structures include piperazine-1,4-diazacycloheptane, 1-(2'-aminoethyl)piperazine, 1-[2'-(2'- '-aminoethylamino)ethyl]piperazine, 1,11-diazacycloeicosane, 1
, 15-diazacyclooctacosane, etc.

In addition, there is another group of linear polyamines having 2 to 8 carbon atoms, such as ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, and octamethylenediamine, and branched fatty acids. Examples of the group polyamines include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine.

Also included are other classes of polyether polyamines, such as polyether diamines and polyether triamines. Also included are phenol-formalin modified products of the polyamines. Also included are those in which the polyamines and the epoxy resin are adducted with an excess of the polyamines. Further, cyanoethylated polyamines of the above-mentioned polyamines with acrylonitrile and the like are also included. Also included are mixtures of two or more of the above polyamines.

Phenols (iii-
1) may be monocyclic or polycyclic, mononuclear or polynuclear, and may be substituted with a halogen atom, nitro group, alkyl group, alkoxy group, etc., or may be unsubstituted; Among the phenols, the preferred one is HO
-(Ar)-(X)m (In the formula, Ar represents an aromatic residue, and X represents a nuclear-substituted halogen atom, an alkyl group, or an alkoxy group. However, different groups within the same molecule may be included. m is a number from 0 to a number 1 less than the number of substitutable hydrogen atoms in Ar. Here, aromatic residues may be mononuclear or polynuclear, monocyclic or polycyclic. It is a monohydric phenol (iii-1-1) represented by (iii-1-1).

Phenols represented by the above general formula (ii
i-1-1) is a phenolic compound having at least one unsubstituted reactive position in the aromatic nucleus, and preferred examples include naphthol carbonate, the following alkylphenols, halogen-substituted phenols,
Such as alkoxyphenols.

Examples of the alkylphenol include ortho-meta- or para-cresol, para-tert-butylphenol, octylphenol, nonylphenol, xylenol, and ethylphenol.

Examples of halogen-substituted phenols include chlorophenol, and examples of alkoxyphenols include anisole.

Another preferable group of such phenols has the general formula

[0098]

[C23]

(In the formula, R1 is an alkylene group having 1 to 3 carbon atoms, R2 and R3 may be the same or different, and are hydrogen atom, methyl group, ethyl group, n-propyl group, n-butyl group) A polynuclear dihydric phenol, such as a hydrogen atom or an alkyl group such as a group, n-hexyl group, n-octyl group, etc.), which has at least one reactive position that is not substituted with an aromatic nucleus. It is a polynuclear dihydric phenol (iii-1-2).

[0100] Such polynuclear dihydric phenol (iii-1-
2) is preferably substituted or unsubstituted 2,2-bis(4-hydroxyphenyl)propane having at least one unsubstituted reactive position on the aromatic nucleus.

[0101] In addition, such phenols (iii-1
) include mononuclear polyhydric phenols such as resorcinol and other polynuclear polyhydric phenols such as bisphenol.

Furthermore, since the reactive position in the aromatic nucleus is usually the ortho or para position relative to the phenolic hydroxyl group, the position that is not substituted at the ortho or para position relative to the hydroxyl group, that is, the hydrogen At least 1 atom
Preferably, the phenols have the same properties. A reaction composition obtained using such a phenol has good compatibility with an epoxy resin.

Next, the carbonyl compound (iii-) used for producing the reaction product (iii) of the present invention is
2) is a -CHO group in the molecule, or

[0104]

[C24]

It is a compound having one or more of the following.

Examples of such carbonyl compounds include formaldehyde, paraformaldehyde, crotonaldehyde, acetaldehyde, furfurylaldehyde,
Examples include adipaldehyde, succinic aldehyde, glyoxal, and acetone.

A preferred group of such carbonyl compounds are aldehydes and reactive derivatives of aldehydes, such as formaldehyde, paraformaldehyde,
Examples include aliphatic lower aldehydes such as acetaldehyde and chloral, with formaldehyde or its reactive derivatives being particularly preferred. Further, for example, formaldehyde and the like can be used in the form of an aqueous solution or a solution in an organic solvent such as methanol.

[0108] Furthermore, the following general formula R-NH-CH2-CH2-CH2-CH2-NH2 (in the formula,
The alkyl trimethylene diamine (iii-3) represented by R is an alkyl group having 8 to 22 carbon atoms is one obtained by reacting a primary monoamine with acrylonitrile and adding hydrogen, as shown in the reaction formula below. Yes, during the ceremony
R represents an alkyl group having 8 to 22 carbon atoms, an octyl group,
2-ethylhexyl group, dodecyl group, coconut oil alkyl group, tetradecyl group, hexadecyl group, octadecyl group,
These include beef tallow alkyl group, oleyl group, and soybean alkyl group.

[0109]

[C25]

[0110] The reaction method for producing the reaction product (iii) of the present invention includes carbonyl compound (iii-2)
Although it can be produced by a one-step reaction method involving all the reaction components of , alkyltrimethylene diamine (iii-3), and phenol (iii-1), a reaction method divided into two or more steps is preferable. For example, Phenols(
iii-1) and alkyltrimethylene diamine (iii
The carbonyl compound (iii-2) may be added to the mixture with the phenol (iii-3).
1) and a carbonyl compound (iii-2) are reacted in advance, and then the resulting reaction product is reacted with an alkyl trimethylene diamine (iii-3). It can also be produced by a method of reacting the compound (iii-2) in advance and then reacting the obtained reaction product with the phenol (iii-1).

[0111] Further, during the production of this reaction product, a compound capable of reacting with the carbonyl compound (iii-2), such as xylene, may be added.

The blending ratio of the phenol (iii-1), carbonyl compound (iii-2) and alkyltrimethylenediamine (iii-3) is as follows. That is, the carbonyl compound (iii-2) is a phenol (i
ii-3) in an amount that is not stoichiometrically excessive, and in an amount of 1 mol or more per 1 mol of the phenol (iii-1), and the alkyltrimethylenediamine (iii-
3) is in an amount of 1 mol or more per 1 mol of phenol (iii-1), and is in an amount that is not stoichiometrically excessive. Preferably phenol (iii-1)/carbonyl compound (iii-2)/alkyltrimethylenediamine (
iii-3) = 1 mol/1 to 3 mol/1 to 3 mol.

[0113] There is no particular restriction on the reaction temperature when reacting the phenol (iii-1) with the carbonyl compound (iii-2) and the alkyltrimethylene diamine (iii-3), but the reaction temperature is not particularly limited. It is preferable to add the compound to the reaction system at a temperature of 40° C. or lower, and then raise the temperature after adding the entire amount to complete the reaction. In this case, 40
The reaction has already started when it is added below ℃,
The temperature may be raised to complete the reaction. After the reaction has finished, by heating the reaction mixture under reduced pressure,
The reaction product can be recovered by removing water, unreacted components, and solvent if present.

Further, the mixing ratio of the epoxy resin (i), the polyamines (ii) and the reaction product (iii) in the curable epoxy resin composition of the present invention is preferably epoxy resin (i)/polyamines ( ii)/reaction product (ii)
i) =40-90/40-9/20-1 (wt%). If the amount of reaction product (iii) exceeds 20%, the physical properties will deteriorate, and if it is less than 1%, there will be no effect, which is not preferred.

[0115] Further, other curing agents and other additives may be added to the curable epoxy resin composition according to the present invention, if necessary. Examples of such additives include, for example, silica powder, bitumen, cellulose, glass fiber, clay,
Examples include mica, aluminum powder, Erosil and the like.

[0116]

[Effect of the invention] As described above, (i), (ii) and (ii)
The curable epoxy resin composition of the present invention containing the component i) has an amine brushing property under harsh conditions such as high humidity, low temperature, and high temperature, compared to conventional polyamines, polyamides, or various modified products thereof. The whitening phenomenon, rising hardness, and water whitening resistance after gelation were significantly improved.

[0117] Furthermore, Mannich bases using phenols/polyamines/carbonyl compounds as disclosed in Japanese Patent Publication No. 49-48480, and Mannich bases using polyethylene polyamines or alicyclic diamines/phenols/aldehydes as disclosed in Japanese Patent Publication No. 52-20460. Compared to hardeners, the whitening phenomenon was significantly improved in the surface amine brush after curing under high humidity and at extremely low temperatures (0 to 5°C) and in the water resistance whitening test after low temperature short-time curing.

Therefore, the curable epoxy resin composition of the present invention is useful as a material for civil engineering and construction, such as various paints, floor coverings, binders for resin mortars, and joint materials for paving materials.

[0119]

[Examples] Hereinafter, the effects of the present invention will be specifically shown in Examples and Comparative Examples, but these are not intended to limit the present invention.

Reference Example 1 Coconut oil alkyltrimethylene diamine 26 was placed in a four-necked flask equipped with a thermometer, stirrer, nitrogen inlet tube, and water separator.
Stir and mix 0g and 108g of cresol, set it so that the temperature does not exceed 40℃, and add 81g of 37% formalin.
was added dropwise, aged for 1 hour after dropping, and further raised to 80°C and reacted for 1 hour. After the reaction is complete, dehydrate under reduced pressure to obtain 380g of alkyltrimethylenediamine/phenol compound■
I got it.

Reference Example 2 Using the same reaction apparatus as in Reference Example 1, 320 g of oleyl trimethylene diamine, 41 g of phenol, and 112 g of nonylphenol were stirred and mixed, and 81 g of 37% formalin was added dropwise under the same reaction conditions as in Reference Example 1. The mixture was reacted and dehydrated under reduced pressure to obtain 491 g of alkyltrimethylenediamine/phenol compound (2).

Examples 1 to 4 Adeka Resin EP-4100 (manufactured by Asahi Denka Kogyo Co., Ltd., bisphenol A type epoxy resin, epoxy equivalent: 190) was used as the epoxy resin, metaxylylene diamine and Adeka Hardener EH-220 were used as the polyamines. (manufactured by Asahi Denka Kogyo Co., Ltd., aliphatic polyamine-based Mannich base curing agent, amine value: 355 mgKOH/g) and the alkyltrimethylene diamine/phenol compounds ■ and ■ produced in Reference Examples 1 and 2 were added as shown in Table 1. Mix at the mixing ratio,
A hardening test was conducted. The results are shown in Table 1.

Comparative Examples 1 to 3 The formulation of Example 1 except that the alkyltrimethylenediamine/phenolic compound (■) and (■) of the present invention were removed, and the polyamide curing agent ACR Hardener H-285 (manufactured by ACR Co., Ltd.) was used. , polyamide amine, amine value: 40
A comparative curing test was conducted using 0mgKOH/g). The results are shown in Table 1.

[0124]

[Table 1]

[0125] Compared to Examples 1 to 4, when the alkyltrimethylene diamine/phenol compound of the present invention was not included in the formulation as in Comparative Examples 1 to 3, or when a polyamide curing agent was used, it was clear that The condition of the coating film was poor, and it was inferior in all aspects of film forming properties, repellency, gloss, amine brushing, sweatering, water whitening test, and mortar adhesion strength, and the curable epoxy resin composition of the present invention showed significant improvement. Admitted.

Claims (1)

[Claims] 1. (i) an epoxy resin having an average of more than one adjacent epoxy group in the molecule, (ii) polyamines having one or more active hydrogen atoms bonded to a nitrogen atom, and (iii) an aromatic Phenols (iii-
1) 1 mol or more of carbonyl compound (iii-2) having at least one carbonyl group in the molecule and the general formula R-NH-CH2-CH2-CH2-NH2 per 1 mol.
(wherein R is an alkyl group having 8 to 22 carbon atoms)
3) A curable epoxy resin composition characterized by containing a reaction product obtained by reacting with 1 mol or more.