JPS5830891B2 - Curable epoxy resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a hardening epoxy resin composition.

In detail, the present invention provides flexibility, toughness, arc resistance, tracking resistance, ultraviolet resistance, water resistance, mechanical properties, electrical properties, storage stability, and hardness properties. This invention relates to a resin composition.

As a hardening agent for epoxy resin, alicyclic polyamines such as 4,4'-diaminodicyclohexylmethane, 4
, 4'-diaminodicyclohexylpropane, 3,3/
-dimethyl-4,4'-diaminodicyclohexylmethane (trade name: Laromi C-260, manufactured by BASF), 3-aminomethyl-3,5,5-trimethyl-1-cyclohexylamine (trade name, manufactured by VEBA-CHEMI) phorondiamine), diaminocyclohexane, etc. are useful arsenic compounds.

Compared to aromatic polyamines, these alicyclic polyamines
Because it does not contain benzene nuclei, it has excellent UV resistance, as well as tracking resistance, arc resistance, water resistance, and dielectric properties (Plastics, 2348, 109).
.

Furthermore, compared to aliphatic polyamines, ring polyamines have a cycloalkyl group in their main chain, and therefore have superior heat resistance and mechanical strength.

Furthermore, compared to alicyclic aliphatic polyamines and spiroacecool polyamines, alicyclic polyamines have amine groups directly bonded to cycloalkyl groups, so when the epoxy resin is hardened, the crosslinking point structure becomes more It is strong and has excellent heat resistance and mechanical properties.

Thus, alicyclic polyamines have particularly good arc resistance,
Epoxy resin sand for insulating materials for electronic and electrical parts that require tracking resistance and mechanical and electrical reliability, and for outdoor insulating materials [has properties useful as an arsenic agent].

However, these alicyclic polyamines are crystalline or have the tendency to crystallize at room temperature or lower, and must be passed through a dissolution process when casting an epoxy resin, which significantly impairs workability. Inferior.

Furthermore, alicyclic polyamines generally tend to absorb water and carbon dioxide gas in the air and have poor storage stability.

In addition, a so-called frosting phenomenon may occur on the hard surface of the epoxy resin due to moisture absorption.

Furthermore, in the field of manufacturing electrical parts, 60 to 130°C
Potting with medium-temperature hardening is widely carried out, but epoxy resin sand [alicyclic polyamine as a hardening agent is hard [
Due to the large amount of heat generated during heating, phenomena such as breakage of the insert, separation from the case due to shrinkage, and cranking may occur.
This makes the module unbearable to use.

In order to improve the above drawbacks, an epoxy-modified aromatic polyamine may be mixed with the alicyclic polyamine.

However, in this case, in order to obtain a stable liquid hardening agent, it is necessary to add aromatic polyamine in an amount of 50% by weight or more (hereinafter simply referred to as %) based on the total polyamine. Only a hardening agent with poor ultraviolet resistance and high viscosity can be obtained.

The object of the present invention is to overcome such drawbacks and to provide an epoxy resin sand [curable epoxy resin composition containing an arsenic] which contains less than 30% of aromatic polyamines in all polyamines, has excellent liquid stability, and has a low viscosity. Our goal is to provide the following.

Another object of the present invention is to provide medium-temperature hardness (replaceability, toughness, arc resistance, tracking resistance, water resistance, ultraviolet resistance, mechanical properties, electrical properties, and storage stability) in the field of manufacturing electrical parts. An object of the present invention is to provide a curable epoxy resin composition with excellent properties.

The curable epoxy resin composition of the present invention contains the following components (I) and (II) as essential components.

(■T average - Epoxy resin having more than one adjacent epoxy group per molecule (■): Formula (wherein R is a divalent carbon 1 arsenic residue having 1 to 10 carbon atoms, m
is an aromatic polyamine (II-1) represented by the formula (wherein R is a divalent carbon f arsenide residue having 1 to 10 carbon atoms, m
is an alicyclic polyamine (II-2) whose average is a number of O to 5) and an epoxy compound (II-3) having an average of one or more adjacent epoxy groups in one molecule. Epoxy-modified polyamino compound obtained at least.

Preferably, the epoxy resin (I) has an average number of more than one substituted or unsubstituted glycidyl ether group in the molecule (where Z is a hydrogen atom, a methyl group, or an ethyl group). Epoxy resin (I-1) 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), an epoxy resin ( I-
3) etc. are included.

The epoxy resin (I-1) having more than one substituted or unsubstituted glycidyl ether group in the molecule is an epoxy resin obtained by heating a phenolic hydroxyl group with a glycidyl ether and an epoxy resin obtained by heating an alcoholic hydroxyl group with a glycidyl ether. Preferred examples of the epoxy resin (I-1) include polyhydric phenols having one or more aromatic nuclei or at least one fatty acid. Polyglycidyl ether (I-1-1) of a polyhydric alcohol having a cyclic nucleus, a polyhydric phenol having one or more aromatic nuclei, or a polyhydric alcohol having at least one alicyclic nucleus and carbon number 2~
Polyglycidyl ethers of alcoholic hydroxyl compounds derived by addition reaction with four alkylene oxides (Cl-1-2) or polyglycidyl ethers of other aliphatic polyhydroxyl compounds (Cl-1-2) -1-
3) etc.

However, polyglycidyl ether (I-1-1) is
For example, a polyhydric phenol (A-1) having at least one aromatic nucleus or a polyhydric alcohol (A-2) having at least one alicyclic nucleus and epihalohydrin (b) are combined with sodium hydroxide. An epoxy resin containing as a main reaction product a polyglycidyl ether obtained by a conventional reaction in the presence of a reaction amount of a basic catalyst or a basic arsenic compound, which contains at least one aromatic nucleus. or a polyhydric alcohol having at least one alicyclic nucleus (A-2) and three parts of epihalohydrin (b) [presence of a catalytic amount of an acidic catalyst such as arsenic]. An epoxy resin such as the one obtained by reacting a polyhalohydrin ether obtained by reacting the following with a basic compound such as hysodium hydroxide, or having at least one aromatic nucleus. Polyhydric phenol (A-1) or at least 1
A polyhalohydrin ether obtained by reacting a polyhydric alcohol (A-2) having 3 alicyclic nuclei with epihalohydrin (b) in the presence of a catalytic amount of a basic catalyst such as triethylamine and water. It is an epoxy resin obtained by reacting an acid with a basic compound such as hysodium.

Similarly, polyglycidyl ether (I-1-2) or polyglycidyl ether (I-1-3) is, for example, polyhydric phenol (A-1) having at least one aromatic nucleus or polyhydric phenol (A-1) having at least one aromatic nucleus. Polyhydric alcohol having an alicyclic nucleus (A
-2) and an alkylene oxide having 2 to 4 carbon atoms.
B) or aliphatic polyhydroxy [arsenic compound (C) and epihalohydrin (b) are reacted in a conventional manner in the presence of an amount of an acidic catalyst such as arsenic with a polyhalohydrin ether and water. It is an epoxy resin containing as a main reaction product a polyglycidyl ether obtained by reacting it with a basic compound such as sodium chloride.

Furthermore, the polyglycidyl ether of an alcoholic polyhydroxy compound derived by an addition reaction between a polyhydric alcohol having at least one alicyclic nucleus or an alkylene oxide having 2 to 4 carbon atoms is Polyhydric phenol having aromatic nucleus or it and carbon number 2-4
It is also possible to obtain an alicyclic nucleus by hydrogenating the aromatic nucleus of the polyglycidyl ether of the alcoholic polyhydroxyr-hydrocarbon compound derived by the addition reaction with alkylene oxide.

Examples of catalysts that can be used in this case include catalysts in which rhodium or ruthenium is supported on a carrier as described in Japanese Patent Publication No. 7788/1983.

The polyhydric phenol (A-1) having at least one aromatic nucleus in this X includes a mononuclear polyhydric phenol (A-1-1) having one aromatic nucleus and two or more aromatic There is a polynuclear polyhydric phenol (A-1-2) having a group nucleus.

Examples of mononuclear polyhydric phenols (A-1-1) include resorcinol, 4,6-dichloro-resorcinol, hydroquinone, 2-promohydroquinone, pyrocatechol, phloroglucinol, ■,5-dihydroxy Examples include naphthalene, 2,7-cyhydrokidinaphthalene, and 2,6-cyhydrokidinaphthalene.

Examples of the polynuclear polyhydric phenol (A-1-2) include the general formula [wherein Ar is an aromatic divalent carbon such as a naphthyl group and a phenylene group (arsenic, for the purpose of the present invention)]. Nylene group is preferred.

Y' and Yl may be the same or different, and include a methyl group, n-propyl group, n-butyl group, n-hexyl group,
Alkyl groups, preferably with up to 4 carbon atoms, such as n-octyl, or halogen atoms, i.e. chlorine, bromine, iodine or fluorine, or methoxy, methoxymethyl, ethoxy, ethoxyethyl groups , n-butoxy, amyloxy, preferably those having up to 4 carbon atoms.

When a substituent other than the hydroxyl group is present on the above-mentioned aromatic divalent carbon [at or both sides of the arsenic group, these substituents may be the same or different.

m and 2 are integers having a value from 0 (zero) to the maximum value corresponding to the number of hydrogen atoms in the aromatic ring (Ar) that can be substituted by a substituent, and may be the same or different values.

R1 is, for example, -5O2- or an alkylene group such as a methylene group, an ethylene group, a trimethylene group, a tetramethinone group,
pentamethylene group, hexamethylene group 2//-ethylhexamethylene group, occumenalene group, nonamethylene group,
Decamethylene group or alkylidene group such as ethylidene group, propylidene group, impropylidene group, imbutylidene group, amylidene group, imbutylidene group, 1-phenylethylidene group or cycloaliphatic group such as 1,4-cyclohexylene group, 1, 3- Cyclohexylene group, cyclohexylidene group or halogen [substituted alkylene group** or halogen (substituted cycloaliphatic group or alkoxy- and aryloxy-substituted alkylidene group) or alkoxy- and aryloxy-substituted alkylene groups or alkoxy- and aryloxy-substituted cycloaliphatic groups, such as methoxymethylene groups,
Ethoxymethylene group, ethoxyethylene group, 2-ethoxytrimethylene group, 3-engineered 14-cypencumethylene group, 1
y 4 (2-methoxycyclohexane) group, phenoxyethylene group, 2-phenyltrimethylene group, 1.
3-(2-phenoxycyclohexane) group or alkylene, ll'J is phenylethylene group, 2-phenyltrimethylene group, 1,7-phenylpentamethylene group,
2-phenyldecamenalene 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 alkyl-substituted Aromatic groups such as 1,4-(2
-methylphenylene) group, ■, 4-(2-ethylphenylene) group, 1,4-(2-n-propylphenylene) group, ', 4 (2n=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 substituted with a hydrogen atom, a hydroxyl group, or an epoxy group) A divalent group such as a carbon [arsenic group] which may be substituted with a divalent carbon [arsenic group], or a divalent group such as a carbon [arsenic group] which may be expressed by the formula It can be rings fused together, or R1 can be a polyalkoxy group, such as polyethoxy, polypropoxy, polythioethoxy, polybutoxy, polyphenylethoxy, or R1 can be a group containing a silicon atom, such as a polydimethylsiloxy group, a polydiphenylsiloxy group, a polymethylphenylsiloxy group,
Alternatively, R1 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 dihydric phenols.

Particularly preferred among the polynuclear dihydric phenols are:
General formula (wherein Y' and ¥1 have the same meanings as above, m and 2 have values of O to 4, and R1 preferably represents an alkylene group or alkylidene group having 1 to 3 carbon atoms, or A saturated group represented by the formula, q is O 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, Screw(
4-hydroxyphenyl)methane, bis(4-hydroxy-2,6-dimethyl-3-methoxyphenyl)methane, ■, 1-bis(4-hydroxyphenyl)ethane, 1
, 2-bis(4-hydroxyphenyl)ethane, 1,1
-bis(4-hydroxy-2-chlorophenyl)ethane, 1,1-bis(3,5dimethyl-4-hydroxynaphthyl)ethane, 1°3-bis(3-methyl-4-hydroxynaphthyl propane), 2 , 2-bis(3,5-dichloro-4-hydroxyphenyl)propane, 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane, 2゜2-bis(3-phenyl-4-hydroxy) phenyl)propane, 2,2-bis(3-isopropyl-
4-hydroxyphenyl)furopane, 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)
-hydroxyphenyl)methane, bis(4-hydroxyphenyl)cyclohexylmethane, 1,2-bis(4-
Hydroxyphenyl)-1,2-bis(phenyl)furopane, 2,2-bis(4-hydroxyphenyl)-1-
bis(hydroxyphenyl)alkanes such as phenylpropane or 4,4'-dihydroxybiphenyl) Ii,
4, 4'-dihydroxyoctachlorobiphenyl, 2
, 2'-dihydroxybiphenyl, 2,4'-dihydroxybiphenyl or bis-(4-hydroxyphenyl)sulfone, 2,4'-
Dihydroxydiphenylsulfone, chlor-2,4-dihydroxydiphenylsulfone, 5-chloro-4,4'
-dihydroxydiphenylsulfone, 3'-chloro-4
, 4'-dihydroxydiphenyl sulfone or bis(4-hydroxyphenyl) ether, 4,3'-(also 4°/-
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-cymethoxy Di(hydroxyphenyl) ethers such as cydiphenyl ether, 4,4'-dihydroxy-2,5-jethoxydiphenyl ether, and 1,1-bis(4-hydroxyphenyl)-2-phenylethane, 1
,3゜3-1-IJ Methyl-1-(4-hydroxyphenyl)-6-hydroxyindan, 2,4-bis(
p-hydroxyphenyl)-4-methylpencune is also suitable.

Furthermore, another preferred group of such polynuclear dihydric phenols has the general formula (5, 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 is O~4), such as 1,4-bis(4-hydroxybenzyl)benzene, 1,4-bis(
4-hydroxybenzyl)tetramethylbenzene, 1,
Examples include 4-bis(4-hydroxybenzyl)tetraethylhensen, 1,4-bis(p-hydroxycumyl)benzene, and 1°3-bis(p-hydroxycumyl)benzene.

Other polynuclear polyhydric phenols (A-1) include, for example, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, initial condensates of phenols and carbonyl [arsenic compounds] (Example: phenol resin initial condensate, condensation reaction product of phenol and acrolein,
Condensation reaction products of phenol and glyoxal, condensation reaction products of phenol and pentanediallyl, condensation reaction products of resorcinol and acetone, initial condensation of xylene-phenol-formalin), phenols and polychloromethyl Examples include condensation products of compounds (eg, condensation products of phenol and bischloromethylxylene).

Here, as the polyhydric alcohol (A-2) having at least one alicyclic nucleus, mononuclear polyhydric alcohol (A-2-1) having one alicyclic nucleus and two There is a polynuclear polyhydric alcohol (A-2-2) having the above alicyclic nucleus.

Preferred examples of the mononuclear polyhydric alcohol (A-2-1) include the general formula (wherein, the person is a cyclohexane residue and a methyl group, n-propyl group, n-butyl group, or n-hexyl group). , an alkyl group such as an n-octyl group, preferably with up to 4 carbon atoms, or a halogen atom, i.e. a chlorine, bromine or fluorine atom, or a methoxy, methoxymethyl, ethoxy, ethoxyethyl group, n - An alkoxy group such as a butoxy group or an amyloxy group, which may or may not be substituted with an alkoxy group having up to 4 carbon atoms, but from the viewpoint of flame resistance, halogen substitution or no substitution. is preferred; O R1 and R3 may be the same or different and may be an alkyl group such as methyl, n-propyl, n-butyl, n-hexyl, n-octyl, preferably up to 6
an alkyl group having 5 carbon atoms, where n and m are 05
1 is 1, preferably 0), such as 1,4-cyclohexanediol, 2-chloro-1,4-cyclohexanediol, 1, 3
-cyclohexanediol, substituted or unsubstituted cyclohexanediols such as 2-methyl-1,4-cyclohexanediol, and 1,4-dihydroxymethylcyclohexane, 2-chloro-1,4-dihydroxymethylcyclohexane, 1,3-dihydroxy Methylcyclohexane, 1.4-
Substituted or unsubstituted dihydroxyalkylcyclohexanes include dihydroxyethylcyclohexane, 1,3-dihydroxydiethylcyclohexane, 1,4-dihydroxypropylcyclohexane, and 1,4-dihydroxybutylcyclohexane.

Furthermore, other mononuclear polyhydric alcohols having one ring group residue include 1.3-cyclopencundiol, 1.3-cyclohebutanediol, 1.4-cyclohebutanediol, 1.4- cyclohebutanediol, 1,5-perhydronaphthalene diol, 1,3-dihydroxy-2,2,4,4-tetramethylcyclobutane, 2,6-dihydrohydronaphthalene, 2,
Other substituted or unsubstituted cycloalkyl polyols such as 7-dihydrocydecahydronaphthalene, 1,5-dihydrocydecahydronaphthalene, and 1,3-dihydroxymethylcyclopenkune, 1,4-
Dihydroxymethylcyclohebutane, 2,6-bis(hydroxymethyl)-decahydronaphthalene, 2,7-bis(hydroxymethyl)decahydronaphthalene, 1,5
-bis(hydroxymethyl)-decahydronaphthalene,
1,4-bis(hydroxymethyl)-decahydronaphthalene, 1,4-bis(hydroxymethyl)-bicyclo(
2,2,2)Octane, other substituted or unsubstituted polyhydroxyalkylcycloalkanes such as dimethyloltricyclotecane.

Among these mononuclear polyhydric alcohols, 1,4-dihydroxymethylcyclohexane is particularly preferred mainly for economic reasons.

Examples of polynuclear polyhydric alcohols (A-2-2) include the general formula: [where A1 and A2 are monocyclic or polycyclic divalent alicyclic hydrocarbon residues, methyl group, n- Alkyl groups, preferably with up to 4 carbon atoms, such as propyl, n-butyl, n-hexyl, n-octyl, or halogen atoms, i.e. chlorine, bromine or fluorine atoms, or methoxy groups; Alkoxy groups such as methoxymethyl, ethoxy, ethoxyethyl, n-butoxy, amyloxy, preferably with alkoxy groups having up to 4 carbon atoms, etc. may be substituted;
Although it is not necessary to use halogen substitution, from the viewpoint of flame resistance, halogen substitution or non-substitution is preferable.

Either k and 1 are O or 1, and both 1 cannot be O.

O2 or alkylene groups such as methylene group, ethylene group, trimethylene group, isopropylene 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, impropylidene group, isobutylidene group, amylidene group, isobutylidene group, 1-phenylethylidene group or cycloalilidene group Groups such as 1,4-cyclohexylene, 1,3-cyclohexylene, cyclohexylidene or halogenated alkylene or halogenated alkylidene groups or halogenated cycloaliphatic groups or alkoxy- and aryl oxy-substituted alkylidene groups or alkoxy- and aryloxy-substituted alkylene groups or alkoxy- and aryloxy-substituted cycloaliphatic groups, such as methoxymethylene, ethoxymethylene, ethoxyethylene groups,
2-ethoxytrimethylene group, 3-ethoxypentamethylene group, 1.4-(2-methoxycyclohexane) group,
phenoxyethylene group, 2 phenoxytrimethylene group,
1.3-(2-phenoxycyclohexane) group or alkylene group Examples: evaphenylethylene group, 2-phenyltrimethylene group, 1-phenylpentamethylene group, 2-phenyldecamethylene group or aromatic group such as phenylene group, naphthylene group Or a halogenated aromatic group such as 1,4-(2-chlorophenylene) group, 1,4
-(2-butylphenylene) group, 1.4-(2-fluorophenylene) group Al or alkoxy- and aryloxy-substituted aromatic group such as 1.4-(2-methoxyphenylene) group, 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, or R2 is a divalent group such as a divalent hydrocarbon group such as may be a ring fused to one of the alicyclic residues, or R2 may be a polyalkoxy group such as a polyethoxy group, a polypropoxy group, a polythioethoxy group, a polybutoxy group, a polyphenylethoxy group. or R2 can be a group containing a silicon atom, such as a polydimethylsiloxy group, a polydiphenylsiloxy group, a polymethylphenylsiloxy group, or R2 can be a group containing a tertiary aromatic term.
-Amino group Can be two or more alkylene groups or alkylidene groups separated by an ether bond, a carbonyl group, or a bond containing sulfur such as sulfur or sulfoxide, but from the viewpoint of heat resistance etc., methylene group, Preferably, it is an ethylene group or an isopropylene group.

j is O or 1.

R1 and R3 may be the same or different, for example an alkyl group such as methyl, n-propyl, n-butyl, n-hexyl, n-octyl, preferably having up to 6 carbon atoms. It is an alkyl group, and n and m are O or 1, preferably O.

i is a number of 0 or more, preferably 0 or 1].

Among these polynuclear polyhydric alcohols (A-2-2), particularly preferred is the general formula: % formula % (31) (wherein AI 1 A2 and R2t J are the above general formula (3
) is a polynuclear dihydric alcohol represented by the same definition as in ).

Preferred examples of polynuclear dihydric alcohols include, for example, 4
, 4'-bicyclohexanediol, 3゜3'-bicyclohexanediol, octachloro-4,4'-bicyclohexanediol, substituted or unsubstituted bicycloalkanediols, or 2゜2-bis-(4-hydroxycyclohexyl ) propane, 2,4'-dihydroxydicyclohexylmethane, bis-(2-hydroxycyclohexyl)-methane, bis-(4-hydroxycyclohexyl)-methane, bis-(4-hydroxy-2゜6)
-Simethyl-3-methoxycyclohexyl)methane, 1
, 1-bis-(4-hydroxycyclohexyl)-ethane, 1,1-bis(4-hydroxycyclohexyl)propane, 1,1-bis(4-hydroxycyclohexyl)butane, 1゜1-bis(4-hydroxycyclohexyl) ) Pentane, 2,2-bis(4-hydroxycyclohexyl)butane, 2,2-bis(4-hydroxycyclohexyl)penkune, 3,3-bis=(4hydroxycyclohexyl)-penkune, 2,2bis-(4 -hydroxycyclohexyl)-heptano, bis-(4-hydroxycyclohexyl-phenylmethane, bis-(4-hydroxycyclohexyl)-cyclohexylmethane, ■
, 2bis-(4-citroxycyclohexyl)-1゜2
-bis-(phenyl)-propane, 2,2-bis-(4
~hydroxycyclohexyl)-1-phenylpropane, 2,2-bis(4-hydroxy-3-methyl-cyclohexyl)propane, 2゜2-bis(4-hydroxy-
2-Methyl-cyclohexyl)furopane, 1,2-bis-(4-hydroxycyclohexyl)-ethane, 1,1
-bis-(4-hydroxy-2-resichlorohexylethane, 1,1-bis-(3,5-dimethyl4-hydroxycyclohexyl)-ethane, 1゜3-bis-[3-
methyl-4-hydroxycyclohexyl)-propane,
2,2-bis(3,5dichloro-4-hydroxycyclohexyl)furopane, 2,2-bis-(3-phenyl-
4-hydroxycyclohexyl)-propane, 2,2-
Bis-(3-isopropyl-4-hydroxycyclohexyl)-propane, 2,2-bis-(2-isopropyl-4-hydroxycyclohexyl)propane, 2,2-
bis-(hydroxycycloalkyl) alkanes such as bis-(4-hydroxyperhydronaphthyl)-propane or 4°4'-dihydroxybicyclohexane,
2,2'-dihydroxybicyclohexane-dihydroxybicycloalkanes such as 2,4-dihydroxybicyclohexane or bis-(4-hydroxycyclohexyl)-sulfone, 2,4'-dihydroxydicyclohexylsulfone, chlor-2, 4dihydroxydicyclohexylsulfone, 5-chloro-4,4'-dihydroxydicyclohexylsulfone, 3'-chloro-4,4
di(hydroxycycloalkyl) sulfones such as '-dihydroxydicyclohexyl sulfones or bis-
(4-hydroxycyclohexyl)ether, 4.3'
-(or 4,2'- or 2,2' or 2,3'-dihydroxy-dicyclohexyl)ether, 4,4'-
Dihydroxy-2,6-dimethyl dicyclohexyl ether, bis-(4-hydroxy-3-inbutylcyclohexyl)-ether, bis-(4-hydroxy-3-isopropylcyclohexyl) ether, bis-(4-hydroxy-3-chlor) cyclohexyl)-ether, bis-(4-hydroxy-3-fluorocyclohexyl)
-ether, bis-(4-hydroxy-3-bromocyclohexyl)-ether, bis-(4-hydroxyperhydronaphthyl)-ether, bis-(4-hydroxy-
3-Chlorperhydronaphthyl) ether, bis-(2
-hydroxybicyclohexyl)-ether, 4,4'
-dihydroxy-2゜6-simethoxydicyclohexyl ether, 4゜4'-dihydroxy-2,5-jethoxydicyclohexyl ether, and also 1,1-bis(4 -hydroxycyclohexyl)-2-phenylethane, 1,3,3-trimethyl-1-(4hydroxycyclohexyl)-6-hydroxyindan, 2,4-bis-(, p-hydroxycyclohexyl)-4-methylpentane Appropriate.

Furthermore, another preferred group of polynuclear polyhydric alcohols (J-2-2) has the general formula: % formula % (32) (in the formula A11 A2) R2 and J are the general formula ( 3)
It is the same as the definition in , and two R2, two j, and two A2 may be different from each other),
For example, 1,4-bis(4-hydroxycyclohexylmethyl)cyclohexane, 1,4-his(4-hydroxycyclohexylmethyl)tetramethylcyclohexane,
1,4-bis(4-t-droxycyclohexylmethyl)
Tetraethylcyclohexane, 1,4-bis(p-hydroxycyclohexylisopropyl)cyclohexane,
Examples include 1°3-bis(p-hydroxycyclohexylisopropyl)cyclohexane.

Furthermore, another preferable group of such polynuclear polyhydric alcohols (A-2-2) has the general formula: % formula % (33) (where AI + A2 + R1+ R2+ R3, j
is the same as the definition in general formula (3) above.

) and substituted or unsubstituted dihydroxyalkylbicycloalkanes such as 4,4'-dihydroxymethyl-bicyclohexane, and 1,2-bis(
4-hydroxymethylcyclohexyl)ethane, 2.2
-substituted or Examples include unsubstituted bis(hydroxyalkylcycloalkyl)alkanes.

Therefore, the polyhydroxyl compound (B) is a polyhydric phenol having at least one aromatic nucleus as described above (
A-1,) or a polyhydric alcohol (A-2) having at least one alicyclic nucleus and an alkylene oxide are reacted in the presence of a catalyst that promotes the reaction between an OH group and an epoxy group. A ROM (
ko”>c (1:R is an alkylene group derived from alkylene oxide) or (and) (R,0)nH (this S
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-1) or the polyhydric alcohol (A-2) to the alkylene oxide is 1:1 (mol: mol) or more, but preferably the polyhydric phenol (A-1) or the polyhydric alcohol (
The ratio of alkylene oxide to OH groups in A2) is 1:1 to 10, preferably 1:1 to 3 (two equivalents).

Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, etc., but those that form a side chain when reacting with the polyhydric phenol (A) to form an ether bond are particularly preferred; Examples include propylene oxide, 1,2-butylene oxide, 1,3-butylene oxide, and 2°3-butylene oxide, with propylene oxide being particularly preferred.

A particularly preferred group of polyhydroxyl compounds (B) are those having the general formula (wherein "Y' ) Yl ) rn 2 Z and R1
is the same as that in formula (1-1) above, and R has 2 carbon atoms.
It is a polyhydroxyl compound represented by ~4 alkylene groups, nl and R2 having values of 1 to 3).

Furthermore, another preferable group of polyhydroxyl compounds as described above has the general formula (wherein R1, R2, R3 and p are the same as those of the above formula (1-2), and R is It is a polyhydroxyl compound represented by a number of 2 to 4 alkylene groups, nl and R2 having values of 1 to 3).

A particularly preferred group of polyhydroxyl compounds having the general formula:
3-1), R is an alkylene group having 2 to 4 carbon atoms, and nl and R2 have values of 1 to 3).

Furthermore, another preferable group of polyhydroxyl compounds has the general formula; R is an alkylene group having 2 to 4 carbon atoms, and nl and R2 have values of 1 to 3).

Among these -nuclear or polynuclear polyhydric alcohols, those having one or two cyclohexane rings as alicyclic residues are particularly preferred, and among them, dihydroxymethylcyclohexane, 2,2-bis(4-citroxycyclohexyl) )-propane is preferred.

In addition, X is an aliphatic polyhydroxyl compound that does not contain a nucleus (O is, for example, ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, diethylene glycol,
Polyhydric alcohols such as glycerin and pentaerythritol, and polyhydric polyhydric alcohols or other active hydrogen-containing compounds (for example, compounds with groups such as amine groups, carboxyl groups, and thiohydroxyl groups) with alkylene oxide added. Examples include polyhydroxyl compounds such as hydroxy compounds and polyether polyols.

In addition, the epihalohydrin (b) in this S is represented by the general formula (in this 5, Z is a hydrogen atom, a methyl group, an ethyl group, and X is a halogen atom); ) Examples include epichlorohydrin, epibromohydrin, 1,2-epoxy-2-
Methyl-3-chloropropane, 1,2-epoxy-2-
Examples include ethyl-3-chloropropane.

Examples of acidic catalysts that promote the reaction between the epihalohydrin (b) and the polyhydroxyl compound (B) or polyhydroxyl compound (0) include Lewis acids such as boron trifluoride, stannic chloride, zinc chloride, and ferric chloride. , derivatives exhibiting these activities (eg, boron trifluoride-ether complex compounds), or mixtures thereof can be used.

Similarly, epihalohydrin (b) and polyhydric phenol (4
Examples of basic catalysts that promote the reaction with ethanolamine), quaternary ammonium compounds (e.g., tetramethylammonium bromide), or mixtures thereof, may be used to form the glycidyl ether simultaneously with such a reaction, or the halo formed as a result of the reaction. Examples of basic compounds that ring-close hydrin ethers by dehydrohalogenation reaction to produce glycidyl ethers include alkali metal hydroxides (e.g., sodium hydroxide), alkali metal aluminates (e.g., sodium aluminate), ) etc. are 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, epoxy resins (2) having on average one or more substituted or unsubstituted glycidyl ester groups in the molecule include aliphatic polycarboxylic acids or aromatic polycarboxylic acids (e.g. phthalic acid, isophthalic acid, terephthalic acid). , tetrahydrophthalic acid, methyltetrahydrofucric acid, hexahydrofucric acid, methylhexahydrofucric acid, endomethylenetetrahydrofucric acid, methylendomethylenetetrahydrophthalic acid, maleic acid, phthalic acid, ichconic acid, succinic acid, glutaric acid , adipic acid, pimelic acid, superric acid, azelaic acid, sebacic acid, dimeric fatty acids, trimellitic acid, trimesic acid, pyromellitic acid, cyclopenkune tetracarboxylic acid, and these halogen-substituted compounds, as well as these polyhydric These include polyglycidyl esters (which may also include terminal carboxyl polyester oligomers obtained from carboxylic acids and polyhydric alcohols), such as glycidyl methacrylates synthesized from epihalohydrin (b) represented by the above general formula and methacrylic acid. It also includes epoxy resins such as those obtained by polymerizing.

In addition, epoxy resins (I
Examples of -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; Condensate (
Examples include epoxy resins obtained from aniline-formaldehyde initial condensate, aniline phenol-formaldehyde initial condensate) and toepihalohydrin (b).

Other epoxy resins (I) include epoxides of compounds having unsaturated double bonds, such as octylene oxide, styrene oxide, butadiene monoepoxide, 1,3-pencdiene monoepoxide, cyclohexene oxide, and cyclohebutene. oxide, cyclooctene oxide, cyclohexadiene monooxide, cycloheptene monooxide, cyclooctadiene monooxide, and the like.

In addition, such epoxy resins (I) include epoxidized products of esters of polycarboxylic acids and alkadiene alcohols (e.g., epoxidized products of diesters of 2,7-octazininol-1 and hexahydrofucric acid), and conjugated diene polymers. Epoxidized products of polymers (e.g., epoxidized polybutadiene, epoxidized styrene-butadiene copolymers, epoxidized acrylonitrile-styrene copolymers), epoxidized products of polymers containing unsaturated bonds (
For example, epoxides of polypropylene, epoxides of polyisobutyne), polyglycidyl ethers of (poly)siloxane, epoxy resins containing heterocycles, epoxy resins in which an epoxy group is bonded to an oxazolidinone ring via a carbon atom, diglycidyl furan. Examples include etherified products, diglycidyl etherified products of dioxane, diglycidyl etherified products of spirobi(m-dioxane), polyepoxy compounds obtained from imidazoene substituted with a polyunsaturated alkenyl group at the 2-position, triglycidyl isocyanurate, etc. It will be done.

Furthermore, as such epoxy resin (I), a group of epoxy compounds represented by the following formula can also be preferably used in the future.

Next, the aromatic polyamine (If-1) represented by the formula (wherein R is a divalent hydrocarbon residue having 1 to 10 carbon atoms, m is a number whose average is O to 5) is aniline 1 0.1 to 15 moles of aldehyde or ketone
It is a condensation product obtained by condensation reaction in a molar ratio, preferably 0.3 to 0.8 molar.

The condensation reaction may be carried out by a known method under acidic conditions. After adding an equivalent amount of the inorganic acid to be coupled to aniline and dissolving it in water, an aldehyde or ketone (preferably an aldehyde or ketone having 1 to 3 carbon atoms) is added while stirring. , particularly preferably formaldehyde), the shrinkage time is increased for 3 to 10 hours at room temperature, then an alkali is added to neutralize, and the aromatic polyamine (■- 1) is obtained.

Furthermore, the alicyclic polyamine (II-2) represented by the formula (wherein R is a divalent hydrocarbon residue having 1 to 10 carbon atoms, m is a number whose average is O to 5) Nuclear hydrogenation of polyamine (IT-1) (
It can be obtained from this.

Nuclear hydrogen addition is performed, for example, as described in British Patent No. 619706 and British Patent No. 718508,
It is carried out according to the usual method for hydrogenating aromatic amines.

That is, aromatic polyamine (TI-) is dissolved in a single or mixed solvent such as methanol, ethanol, propatool, dioxane, cyclohexane, etc. in a pressurized reaction vessel, and ruthenium, platinium, cobalt, nickel, etc. are added as metal catalysts for hydrogenation. Using iron etc., reaction temperature 120~2
40℃ preferably 140~160℃, reaction pressure 120~
2501g/ffl preferably 130-180ky/i
The hydrogenation reaction is carried out for several hours.

After the reaction is completed, the metal catalyst is removed by filtration, and the solvent is distilled off to obtain a pale yellow transparent alicyclic polyamine (II-2) that is viscous and liquid at room temperature.

Next, as the epoxy compound (I[-3), an epoxy compound ([
-3-1), an epoxy compound (II-3-2) having one adjacent epoxy group per molecule, and a mixture of an epoxy compound (I[-3-1) and an epoxy compound (■-3-2) can be mentioned.

Here, the epoxy compound (]]l-3-2' has one substituted or unsubstituted glycidyl ether group represented by the formula (here, Z is a hydrogen atom, a methyl group, or an ethyl group) in the molecule. Epoxy compound (■-3-2-1), containing one substituted or unsubstituted glycidyl ester group represented by the formula Z (where Z is a hydrogen atom, a methyl group, or an ethyl group) in the molecule.
An epoxy compound (■-3-2-2) containing an N-substituted or unsubstituted 1,2-epoxyprobyl group represented by (where Z is a hydrogen atom, a methyl group, or an ethyl group) in the molecule. Epoxy compound having one (1-3-2-3
) and other epoxy compounds (l[-3-2-4)
etc. are included.

Therefore, the epoxy compound ([-3-2-1) can be obtained by reacting an aliphatic monoalcohol, an alicyclic monoalcohol, a -hydric phenol, and an epihalohydrin according to the above-mentioned method for producing epoxy resin (I). can get.

Here, the aliphatic monoalcohol mentioned above has 3 to 3 carbon atoms.
22 aliphatic monoalcohols are preferred, and especially butyl alcohol, allyl alcohol, pentyl alcohol, hexyl alcohol, heptyl alcohol, and octyl alcohol are preferred. 22 alicyclic monoalcohols are preferred, particularly cyclopentyl alcohol, cyclohexyl alcohol, cycloheptyl alcohol, and cyclooctyl alcohol, and as the -valent phenol, m phenols having one or more aromatic nuclei are preferred. Preferably, especially phenol (
carbolic acid), cresol, xylenol, ethylphenol, propylphenol, thymol, carvacrol,
Particularly preferred are butylphenol, amylphenol, octylphenol, and the like.

Further, the epoxy compound (n-3-2-2) can be obtained by reacting an aliphatic, alicyclic or aromatic monocarboxylic acid with an epihalohydrin according to the method for producing the epoxy resin (I) described above.

Here, the aliphatic monocarboxylic acid has 3 to 22 carbon atoms.
Preferred are aliphatic monocarboxylic acids of
Further, as the alicyclic monocarboxylic acid, an alicyclic monocarboxylic acid having 6 to 22 carbon atoms is preferable, and cyclohexane monocarboxylic acid, cycloheptane monocarboxylic acid, and cyclooctane monocarboxylic acid are particularly preferable, and further, As the aromatic monocarboxylic acid, monocarboxylic acids having one or more aromatic nuclei are preferred, in particular benzoic acid, toluic acid, ethylbenzoic acid, trimethylbenzoic acid, cumic acid, 2.3,4,5- Tetramethylbenzoic acid and the like are preferred.

Furthermore, the epoxy compound ([-3-2-3) is aliphatic,
It is obtained by reacting an alicyclic or aromatic monoamine with an epihalohydrin according to the method for producing the epoxy resin (1) described above.

Here, as the aliphatic monoamine, aliphatic monoamines having 3 to 22 carbon atoms are preferable, and among them, butylamine, allylamine, pentylamine, and hexylamine are particularly preferable, and alicyclic monoamines have 5 to 22 carbon atoms.
Of these, alicyclic monoamines such as cyclopentylamine, cyclohexylamine, cycloheptylamine, and cyclooctylamine are particularly preferred.As aromatic monoamines, monoamines having one or more aromatic nuclei in the molecule are preferred. Among these, aniline, toluidine, ethylaniline, propylaniline, xylidine, trimethylaniline and the like are particularly preferred.

Still other epoxy compounds ([-3-2-4) include monoepoxy compounds obtained by reacting olefins or cycloolefins with peracids.

Such epoxy compounds (n-3-2-4) include octylene oxide, styrene oxide, phtadiene monoepoxide, 1,3-pentadiene monoepoxide, cyclohexene oxide, cycloheptene oxide, cyclooctene oxide, and cyclohexadiene. Examples include monooxide, cycloheptadiene monooxide, and cyclooctadiene monooxide.

The epoxy-modified polyamino compound (n), which is an essential component of the curable epoxy resin composition of the present invention, is prepared by the following methods.

That is, 5 to 30 parts by weight of aromatic polyamine (II-1) (hereinafter simply referred to as parts) and alicyclic polyamine ([-2)
Epoxy compound (n-3) to 60 to 100 parts of the mixture
Add 10 to 50 parts and heat to melt until the temperature of the system reaches 15
Stirring is carried out for 2 to 10 hours under conditions not exceeding 0°C to obtain an epoxy-modified polyamino compound 'IMI).

In this case, reaction removal and solvent removal may be performed using a suitable solvent to aid dissolution at low temperatures.

In addition, in order to suppress rapid exothermic reactions, first, a mixture of aromatic polyamine (ll-1) and alicyclic polyamine (n-2) was heated to 60 to 100°C to melt it, and then,
The epoxy compound (■-3) is added dropwise with stirring over a period of 1 to 3 hours, and after the addition is completed, the mixture is further stirred for 1 to 5 hours to obtain the epoxy modified compound (■).

Furthermore, in order to suppress rapid heat generation and obtain a cured product with good physical properties, first, aromatic polyamine (II-1) was added to 60%
A part of the epoxy compound (II-3) to be melted by heating at ~130°C and added thereto was added dropwise with stirring for 30 minutes to 3 hours, and after the dropwise addition was completed, stirring was continued for another 1 to 5 hours to obtain the first stage. As a reaction, alicyclic polyamine (II-2) is added, and the remaining epoxy compound (II-3) is reduced to 60 to 10
0'C, stirred dropwise for 1 to 5 hours, and then stirred for 1 to 5 hours after dropping.
The reaction is terminated by stirring for ~5 hours, and an epoxy-modified polyamino compound (II) can be obtained.

In the above method, the entire reaction may be carried out under a nitrogen stream to prevent discoloration of the reaction product, and a suitable discoloration inhibitor may be added.

The epoxy-modified polyamino compound thus obtained can be used to form a curable epoxy resin composition exhibiting various excellent physical properties by containing an epoxy resin (1) having more than one adjacent epoxy group per molecule on average. give.

It is desirable that the epoxy resin (1) and the epoxy-modified polyamino compound (II) be mixed at a ratio of 0.6 to 1.5 equivalents, preferably 0.8 to 1.3 equivalents of the polyamino compound per equivalent of the epoxy resin. .

Further, other additives may be added to the curable epoxy resin composition according to the present invention as necessary.

Examples of such additives include, for example, silica powder, bitumen, cellulose, glass fiber, viscosity, mica, aluminum powder, yellow seal, talc, bentonite, calcium carbonate, and the like.

The curable composition according to the present invention may contain a non-reactive diluent, a reactive binder, a flame retardant, a flexibilizing agent, and other modifiers as required.

Examples of the flame retardant include halogen flame retardants (eg hexabromobenzene), inorganic flame retardants (eg hydrated alumina, phosphates) and the like.

Further, examples of the non-reactive diluent include dibutyl phthalate, dioctyl phthalate, tetrahydrofurfuryl alcohol, dimethylformamide, etc., and examples of the reactive diluent include butyl glycidyl ether, phenyl glycidyl ether, cresyl glycidyl ether, etc. It will be done.

Examples of the flexibility imparting agent include polysulfide, polyamide, polyalkylene polyol elastomer, and the like.

In addition, as modifiers for adjusting reactivity, viscosity, resorption acidity, hygroscopicity, etc., phenol, cresol, butylphenol, nonylphenol, catechol, hydroquinone, resorcinol, 222-bis(4-hydroxyphenyl)propane, bis( 4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)sulfone, condensation products of phenol and formaldehyde, phenols such as tris(dimethylaminomethyl)phenol, acetic acid,
Examples include carboxylic acids such as benzoic acid, oxalic acid, butyric acid, and stearic acid.

Furthermore, in order to adjust reactivity, pot life, viscosity, hardness, etc., aliphatic amines such as alkylene diamine, polyalkylene polyamine, metaxylene diamine, dialkylaminoalkylamine, menthanediamine, 3,3
'-dimethyl-4,4'-diaminodicyclohexylmethane, 3-aminomethyl-3,5,5-4limethyl-1
- Alicyclic amines such as cyclohexylamine and diaminocyclohexane, cyclic amines such as piperidine, 1-(N-β-hydroxyethyl-4-piperidyl)-3-(4piperidyl)propane, piperazine, and N-aminoethylpiperazine; Metaphenylenediamine 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenyl oxide, 4,4'-diaminodiphenylimine, biphenylenediamine, aromatic amines such as aniline, polyamines containing heterocyclic rings, polyether polyamines , various tertiary amines, alkanolamines, polyamines such as imidazoles, or the above polyamines, and an epoxy compound,
Polyamines obtained by reaction with acrylonitrile, fatty acids, caprolactam, etc., or polyamines such as the aromatic polyamine (n-1), alicyclic polyamine (■2), or the polyamine (II-1), (lI -2)
Polyamines obtained by reaction with acrylonitrile, fatty acids, caprolactam, etc. can be used in combination.

The curing agent made of the epoxy-modified polyamino compound of the present invention has an aromatic polyamine of 30φ or less among all polyamines, and has excellent low viscosity and liquid stability, compared to conventional curing agents.

In addition, since the heat generated during curing is small, it can be suitably used in the production of electrical and electronic parts, whose use has been limited in the past.

Furthermore, the effects of the present invention are that the curable epoxy resin composition has less deterioration such as discoloration and chalking, and has excellent continuity, toughness, arc resistance, tracking resistance, ultraviolet resistance, mechanical properties, electrical properties, and water resistance. It's in giving things.

The present invention will be explained in more detail below using reference examples and examples.

Reference Example for Production of Epoxy-Modified Polyamino Compound Four 100 parts of 1°diaminodiphenylmethane were placed in a flask and melted by heating at 100°C under nitrogen. Then, 40 parts of butyl glycidyl ether was added dropwise over 2 hours, and stirring was continued for 5 hours.

A viscous yellow-brown liquid with an active hydrogen equivalent of 81.9 was obtained.

Take 28 parts of this and add 8 parts of diaminodicyclohexylmethane.
0 parts, add 16 parts of butyl glycidyl ether and heat to 80°C.
, stirring was performed for 5 hours.

A liquid polyamine with an amine equivalent of 72.0 was obtained.

The viscosity at 25°C (the same applies hereinafter) was 32 Stokes.

Reference Example 2 100 parts of diaminodiphenylmethane and 10 parts of butyl glycidyl ether were reacted under the same conditions as in Reference Example 1 to obtain a viscous yellowish brown liquid with an active hydrogen equivalent of 57.1.

Take 33 parts of this and add 8 parts of diaminodicyclohexylmethane.
0 parts and 20 parts of butyl glycidyl ether were added and reacted under the same conditions as in Reference Example 1 to obtain a liquid polyamine with an amine equivalent weight of 69 (viscosity 28 Stokes).

Reference example 3゜20 parts of diaminodiphenylmethane and 80 parts of diaminodicyclohexylmethane were placed in a 4-row flask and melted at 60°C, and then 24 parts of butyl glycidyl ether was added to 90 parts of diaminodicyclohexylmethane.
The mixture was stirred at ℃ for 3 hours while being added dropwise.

A liquid polyamine with an amine equivalent of 71.4 was obtained.

(Viscosity 42 Stokes). Reference example 4゜Condensation product of aniline and formaldehyde (η0.46
70 parts of alicyclic polyamine with an amine value of 480 and 30 parts of diaminodiphenylmethane obtained by adding ) to a water chamber were placed in a fourth flask, stirred at 60°C for 3 hours to melt, and then 50 parts of butyl glycidyl ether were added. The mixture was stirred at 90°C for 3 hours while being added dropwise.

A liquid polyamine with an amine equivalent of 104 was obtained (viscosity 55 Stokes).

Reference example 5゜Condensation product of aniline and formaldehyde (η-3,4
, amine value 535) and 20 parts of an alicyclic polyamine obtained by hydrogenating a condensation product of aniline and formaldehyde (η-0.08, amine value 485) were placed in a flask and heated at 60°C. The mixture was stirred for 3 hours to melt, and then 20 parts of butyl glycidyl ether was added dropwise at 90° C. while stirring for 4 hours.

A liquid polyamine with an amine equivalent of 74.0 was obtained (viscosity 48
Stokes).

Reference example 6゜Condensation product of aniline and formaldehyde (η-2,0
, amine value 539) and 90 parts of an alicyclic polyamine obtained by hydrogenating a condensation product of aniline and formaldehyde (η-2,1, amine value 456) were placed in a flask and heated at 80°C. The mixture was stirred for 4 hours to melt, and then 40 parts of α-olefin oxide having 8 to 10 carbon atoms (epoxy equivalent: 150) was added dropwise at 100° C. while stirring for 5 hours.

A liquid polyamine with an amine equivalent of 100.9 was obtained (viscosity 2
4 Stokes).

Reference example 7゜Condensation product of aniline and formaldehyde (η-0,5
0, amine value 549), 95 parts of alicyclic polyamine obtained by hydrogenating a condensation product of aniline and formaldehyde (η-0,46, amine value 480), and diglycidyl ether of bisphenol A (no Denka EP-41
00) and reacted at 80°C for 3 hours.

A liquid polyamine with an amine equivalent of 65.8 was obtained (viscosity 61
Stokes).

Reference Example 30 parts of 8°diaminodiphenylmethane and 10 parts of butyl glycidyl ether were placed in four flasks and stirred at 90°C for 3 hours under nitrogen.

Next, the condensation product of aniline and formaldehyde (η-
70 parts of alicyclic polyamine with an amine value of 480 obtained by hydrogenating 0.46) and 40 parts of butyl glycidyl ether
1 part of cresol was added to the mixture at 800C over 11 hours, and the mixture was further stirred at 90°C for 2 hours, and then 10 parts of cresol was added.

A liquid polyamine having an active hydrogen equivalent of 104 and a viscosity of 54 Stokes was obtained.

Comparative Reference Example 16 To 25 parts of the adduct of aromatic polyamine and epoxy compound prepared in the first step of Reference Example 1, 75 parts of diaminodicyclohexylmethane was blended.

A yellow-brown liquid with an active hydrogen equivalent of 59 and a viscosity of 41 Stokes (25°C) was obtained.

Comparative Reference Example 2゜65 parts of diaminodicyclohexylmethane were blended with 35 parts of the adduct of aromatic polyamine and epoxy compound prepared in the first step of Reference Example 2.

A yellow-brown transparent liquid with an active hydrogen equivalent of 55 and a viscosity of 93 Stokes (25°C) was obtained.

Comparative Reference Example 3 40 parts of diaminodicyclohexylmethane was blended with 60 parts of the adduct of aromatic polyamine and epoxy compound prepared in the first step of Reference Example 2.

Active hydrogen equivalent: 56, viscosity: 205 Stokes (25°C)
A yellow-brown transparent liquid was obtained.

Comparative Reference Example 4 30 parts of diaminodicyclohexylmethane and 25 parts of butyl glycidyl ether were added to 70 parts of the separated aromatic polyamine and epoxy compound prepared in the first step of Reference Example 1, and 8 parts of butyl glycidyl ether were added.
Stirring was performed at 0°C for 4 hours.

Active hydrogen equivalent: 101. Viscosity 820 Stokes (25℃)
A brown viscous liquid was obtained.

Table 1 shows the physical properties related to the liquid stability described above.

Liquid stability was determined by precipitation of crystals.

Production Examples 1 to 8 of Curable Compositions Comparative Examples 1 to 5 Various epoxy compounds were cured using the epoxy-modified polyamino compounds obtained in the above reference examples and comparative reference examples as a curing agent, and the physical properties after curing were compared. investigated.

Curing conditions were 70°C for 2 hours, followed by 150'C14
It's time.

The formulation and physical properties are shown in Table 2.3.

Claims (1)

[Scope of Claims] 1. A hardening epoxy resin composition (I) characterized by containing the following components (I) and (II) as essential constituents: from 1 per molecule on average Epoxy resin having many adjacent epoxy groups (■): Aromatic polyamine represented by the formula (wherein R is a divalent hydrocarbon residue having 1 to 10 carbon atoms, m is a number whose average is O to 5) (II-1) and the alicyclic polyamine (n-2 ) with an epoxy compound (I[-3) having an average of one or more adjacent epoxy groups in one molecule.