JPH0694496B2 - Curable composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to an epoxy resin curable composition, and more particularly to a curable composition that imparts flexibility to an epoxy resin.

[Conventional technology and problems]

Epoxy resins have been widely used for applications such as paints, electricity, civil engineering and construction, adhesion, etc. However, when ordinary bisphenol A type epoxy resins are cured with polyamines, they lack flexibility and are motor transformers for electricity. When used for casting, etc., cracks occur in the cooling and heating cycle, and this tendency is remarkable especially when casting and molding a complex shape, and the appearance of a flexibility-imparting agent with good thermal shock is desired. It is rare. Further, when used for civil engineering and construction, even if it has good flexibility at room temperature, it tends to lose flexibility at a low temperature of about 0 ° C and become hard and brittle, which causes cracking of the cured product. Has become.

Although various flexibility-imparting agents have been developed and put into practical use for the purpose of improving flexibility, compatibility with bisphenol A type epoxy resin, curability, water resistance, chemical resistance, There are problems in temperature-sensitive properties and physical properties, and each has its advantages and disadvantages.

For example, in the case of dimer acid-modified diglycidyl ether, when used for civil engineering and construction applications, it is not practical because it is eroded by cement-resistant alkaline water, and in the case of polyoxyalkylene glycol diglycidyl ether, it is hardened. The properties are remarkably poor, and the water resistance of the cured product is insufficient.

Furthermore, in the case of BPA-based side chain type flexible epoxy resin, the water resistance and alkali resistance are improved, but the flexibility problem in the low temperature region remains, and the curing is accelerated over time,
When left outdoors for a long time, it is difficult to maintain flexibility.

Further, the flexible thiol compound has a problem of odor. In addition, when it is used for structural adhesion, harsh conditions are required, and it must satisfy the flexibility and adhesiveness (tensile shear strength, T-type peeling) especially in the low temperature region of -30 ° C. .

In order to improve such performance, urethane-modified epoxy resin and rubber-modified (CTBN) -modified epoxy resin have been developed and are already in practical use, but the adhesive strength and flexibility at room temperature are improved, but in the low temperature range. In that case, flexibility tends to be lost, and peel strength tends to be significantly reduced.

However, the curable composition comprising the blocked urethane / epoxy activated organic amine curing agent system of the present invention is an improvement of the above-mentioned drawbacks, and is a conventional flexible epoxy resin, urethane-modified epoxy resin, or rubber-modified epoxy resin. It is characterized by extremely excellent properties such as low-temperature curability, flexibility, and temperature-sensitive properties, especially flexibility at low temperatures, hardness retention with time, water resistance, alkali resistance, and thermal shock resistance.

As a reason for such performance improvement, the conventional epoxy resin-based flexibility-imparting agent, and the urethane-modified epoxy resin and the rubber-modified epoxy resin are mainly compared with each other by the reaction between the epoxy group and the active organic amino group. The resin obtained from the composition of the present invention has a reaction of the above-mentioned epoxy group with an active organic amino group, and further, an isocyanate /
It is considered that the reactions of the amino groups proceed at the same time, the crosslink density is improved, and the urea bond is contained in the molecular crosslinked structure, which contributes to the improvement of the properties.

The curable composition of the present invention is widely applied to applications such as electricity, civil engineering and construction, and adhesion due to its excellent performance.

[Means for solving problems]

The curable composition of the present invention comprises, as an essential component, an epoxy resin having an average of more than one adjacent epoxy groups in the molecule, a polyhydroxy compound, and an excess of polyisocyanate compound, which is an isocyanate group content of 1 to 1. Reaction of a urethane bond-containing compound (-a) having an average molecular weight of 2740 to 3720 (10% by weight) with a compound (b) having a monovalent phenolic hydroxyl group at an NCO / phenolic OH equivalent ratio = 1 / 1.0 to 1.5 Sir,
The isocyanate group of the compound (-a) is replaced by the compound (-
b) A flexibility-imparting agent for epoxy resin consisting of a blocked isocyanate compound obtained by masking with a phenolic hydroxyl group, an active organic amino compound (excluding 1,3-bis (aminomethyl) cyclohexane) curing agent It is characterized by

The epoxy resin having an average of more than one adjacent epoxy group in the molecule used in the present invention is, for example, an epoxy resin having an average of more than one 1,2-epoxy group in the molecule, preferably substituted or non-substituted. An epoxy resin having an average of more than one substituted glycidyl ether group in the molecule,
Epoxy resin having an average of more than one substituted or unsubstituted glycidyl ester group in the molecule, epoxy resin having an average of more than one N-substituted or unsubstituted 1,2-epoxypropyl group in the molecule, epoxidation The polyunsaturated compound described above, and other conventionally known adjacent epoxy group-containing epoxy resin are included.

A preferred example of the epoxy resin (I) having an average of more than one 1,2-epoxy group in such a molecule is represented by the formula: (Wherein Z is a hydrogen atom, a methyl group, an ethyl group) having an average of more than one substituted or unsubstituted glycidyl ether group in the molecule, an epoxy resin (I-1), a formula: (Wherein Z is a hydrogen atom, a methyl group, an ethyl group), an epoxy resin (I-2) having on average more than one substituted or unsubstituted glycidyl ester group in the molecule, formula: (Wherein Z is a hydrogen atom, a methyl group, an ethyl group) and an epoxy resin (I- having an average of more than one N-substituted or unsubstituted 1,2-epoxypropyl group in the molecule) (I-
3) etc.

The epoxy resin (I-1) having more than one substituted or unsubstituted glycidyl ether group in the molecule is an epoxy resin obtained by converting a phenolic hydroxyl group into a glycidyl ether group or an epoxy resin obtained by converting an alcoholic hydroxyl group into a glycidyl ether group. The preferred examples of the epoxy resin (I-1) include polyglycidyl ether (I-1-1) of polyhydric phenol having one or more aromatic nuclei and one or two. Polyglycidyl ether (I-1-2) of alcoholic polyhydroxyl compound and one or two derived from addition reaction of polyhydric phenol having aromatic nucleus and alkylene oxide having 2 to 4 carbon atoms Polyglycidyl ether of polyhydric alcohol C having the above alicyclic nucleus (I-1
-3) and the like.

Then, with polyglycidyl ether (I-1-1),
For example, polyglycidyl ether obtained by reacting polyhydric phenol A having at least one aromatic nucleus with epihalohydrin E in the presence of a basic catalyst such as sodium hydroxide or a reaction amount of a basic compound by a conventional method. An epoxy resin containing at least 1 as a main reaction product
A polyhalohydrin ether obtained by reacting a polyphenol A having one aromatic nucleus with epihalohydrone E in the presence of a triacidic catalytic amount such as boron trifluoride by a conventional method and a base such as sodium hydroxide. Reaction with an epoxy resin or polyhydric phenol A having at least one aromatic nucleus and an epihalohydrin E in the presence of a basic catalyst such as triethylamine in a catalytic amount by a conventional method. It is an epoxy resin obtained by reacting the obtained polyhalo hiroline ether with a basic compound such as sodium hydroxide.

Similarly, the polyglycidyl ether (I-1-2) means, for example, a polyhydroxyl compound B derived by an addition reaction of a polyhydric phenol having at least one aromatic nucleus and an alkylene oxide having 2 to 4 carbon atoms. And epihalohydrin E are obtained by reacting a polyhalohydrin ether obtained by a conventional method in the presence of a catalytic amount of an acidic catalyst such as trifluoroboron with a basic compound such as sodium hydroxide. It is an epoxy resin containing polyglycidyl ether as a main reaction product.

The polyhydric phenol A having at least one aromatic nucleus here is a mononuclear polyhydric phenol (A-1) having one aromatic nucleus and a polynuclear polyhydric phenol having two or more aromatic nuclei. There is (A-2).

Examples of such mononuclear polyhydric phenol (A-1) include, for example, resorcinol, hydroquinone, pyrocatechol, phloroglucinol, 1,5-dihydroxylnaphthalene, 2,7-dihydroxynaphthalene, 2,6-dihydroxynaphthalene. And so on.

Moreover, as an example of polynuclear polyhydric phenol (A-2), a general formula: (In the formula, Ar is an aromatic divalent hydrocarbon such as a naphthylene group and a phenylene group, and a phenylene group is preferable for the purpose of the present invention. Y ′ and Y ₁ may be the same or different, and a methyl group, n- Propyl group, n-butyl group, n-hexyl group,
Alkyl group such as n-octyl group, preferably an alkyl group having a maximum of 4 carbon atoms or a halogen atom, that is, chlorine atom, bromine atom, iodine atom or fluorine atom or methoxy group, methoxyethyl group, ethoxy group, ethoxyethyl group , N-butoxy group, amyloxy group and the like alkoxy group having up to 4 carbon atoms. When a substituent other than a hydroxyl group is present on either or both of the above aromatic divalent hydrocarbon groups, these substituents may be the same or different. m and z are integers having a value from 0 (zero) corresponding to the number of hydrogen atoms of the aromatic ring (Ar) that can be substituted by a substituent to a maximum value, and can be the same or different. R ₁ is for example --O--, --S--, --SO--, --SO _2- , or an alkylene group 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-phenyl Ethylidene group or cycloaliphatic group such as 1,4-cyclohexylene group, 1,3-cyclohexylene group, cyclohexylidene group or halogenated alkylene group, halogenated alkylidene group or halogenated cycloaliphatic group Groups 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, Toxymethylene group, ethoxyethylene group, 2-ethoxytrimethylene group, 3-ethoxypentamethylene group, 1,4- (2-methoxycyclohexane) group, phenoxyethylene group, 2-phenoxytrimethylene group, 1,3- ( 2-phenoxycyclohexane)
Group or alkylene group such as phenylethylene group, 2-
Phenyltrimethylene group, 1-phenylpentamethylene group, 2-phenyldecamethylene group or aromatic such as phenylene group, naphthylene group or halogenated aromatic group such as 1,4- (2-chlorophenylene) group, 1, 4-
(2-Bromphenylene) group, 1,4- (2-fluorophenylene) group or aromatic group substituted with alkoxy and aryloxy, for example, 1,4- (2-methoxyphenylene) group, 1,4- (2- Ethoxyphenylene) group, 1,4-
(2-n-propoxyphenylene) group, 1,4- (2-phenoxyphenylene) group or alkyl-substituted aromatic group such as 1,4- (2-methylphenylene) group, 1,4-
(2-Ethylphenylene) group, 1,4- (2-n-propylphenylene) group, 1,4- (2-n-butylphenylene) group
Group, a divalent group such as a divalent hydrocarbon group such as a 1,4- (2-n-dodecylphenylene) group, or R ₁ is, for example, a compound represented by the formula: It may be a ring fused to one Ar group as in the case of the compound represented by, or R ₁ is a polyethoxy group, a polypropoxy group, a polythioethoxy group, a polybutoxy group, a polyphenylethoxy group. R ₁ can also be a polyalkoxy group such as, or R ₁ can be a group containing a silicon atom such as a polydimethylsiloxy group, a polydiphenylsiloxy group, a polymethylphenylsiloxy group, or R ₁ can be Polynuclear represented by an aromatic ring, which may be two or more alkylene groups or alkylidene groups separated by a tertiary-amino group ether linkage, a carbonyl group or a sulfur-containing linkage such as sulfur or a sulfoxide. There are dihydric phenols.

Of these polynuclear dihydric phenols, particularly preferred are the general formulas (In the formula, Y ′ and Y ₁ have the same meanings as described above, m and z have a value of 0 to 4, and R ₁ is preferably an alkylene group or alkylidene group having 1 to 3 carbon atoms or a formula It is a polynuclear dihydric phenol represented by a saturated group represented by.

Examples of such dihydric phenols are 2,2-bis- (p-hydroxyphenyl) -propane, 2,4'-dihydroxydiphenylmethane, bis- (2-hydroxyphenyl) -methane, commonly referred to as bisphenol A. , Bis- (4-hydroxyphenyl) -methane, bis- (4-
Hydroxy-2,6-dimethyl-3-methoxyphenyl)
-Methane, 1,1-bis- (4-hydroxyphenyl)-
Ethane, 1,2-bis- (4-hydroxyphenyl) -ethane, 1,1-bis- (4-hydroxy-2-chlorophenyl) -ethane, 1,1-bis- (3,5-dimethyl-4- Hydroxyphenyl) -ethane, 1,3-bis- (3-methyl-4-hydroxyphenyl) -propane, 2,2-bis- (3,5-dichloro-4-hydroxyphenyl) -propane, 2,2- Bis- (3-phenyl-4-hydroxyphenyl) -propane, 2,2-bis- (3-isopropyl-4-hydroxyphenyl) -propane, 2,2-bis-
(2-Isopropyl-4-hydroxyphenyl) -propane, 2,2-bis- (4-hydroxynaphthyl) -propane, 2,2-bis- (4-hydroxyphenyl) -pentane, 3,3-bis- ( 4-hydroxyphenyl) -pentane, 2,2-bis- (4-hydroxyphenyl) -heptane, bis- (4-hydroxyphenyl) -methane, bis- (4-hydroxyphenyl) -cyclohexylmethane, 1,2- Bis-, such as bis- (4-hydroxyphenyl) -1,2-bis- (phenyl) -propane and 2,2-bis- (4-hydroxyphenyl) -1-phenylpropane
(Hydroxyphenyl) alkane or 4,4'-dihydroxybiphenyl, 2,2'-dihydroxybiphenyl 2,
Dihydroxybiphenyl such as 4'-dihydroxybiphenyl or bis- (4-hydroxyphenyl) -sulfone, 2,4'-dihydroxydiphenylsulfone, chloro-2,4-dihydroxydiphenylsulfone, 5-chloro-4,4'- Dihydroxydiphenyl sulfone, 3'-
Di- (hydroxyphenyl) -sulfone such as chloro-4,4'-dihydroxydiphenyl sulfone or bis-
(4-hydroxyphenyl) -ether, 4,3 '-(or 4,2'- or 2,2'-dihydroxy-diphenyl) ether, 4,4'-dihydroxy-2,6-dimethyldiphenyl ether, bis- ( 4-hydroxy-3-isobutylphenyl) -ether, bis (4-hydroxy-3-isopropylphenyl) -ether, bis- (4-hydroxy-3-chlorophenyl) -ether, bis- (4-hydroxy-3-). Fluorphenyl) -ether, bis-
(4-hydroxy-3-bromophenyl) -ether,
Bis- (4-hydroxynaphthyl) -ether, bis-
(4-hydroxy-3-chloronaphthyl) -ether,
Bis- (2-hydroxybiphenyl) -ether, 4,
Di- (hydroxyphenyl) -ethers such as 4'-dihydroxy-2,6-dimethoxydiphenyl ether and 4,4'-dihydroxy-2,5-diethoxydiphenyl ether are included, and 1,1-bis- (4 -Hydroxyphenyl) -2-phenylethane, 1,3,3-trimethyl-1-
(4-Hydroxyphenyl) -6-hydroxyindane, 2,4-bis- (p-hydroxyphenyl) -4-methylpentane are also suitable.

Furthermore, another group of such polynuclear dihydric phenols, which is preferred, has the general formula (Here, R ₃ is a methyl or ethyl group, R ₂ is an alkylidene group having 1 to 9 carbon atoms or another alkylene group, and p is 0 to
4), for example 1,4-bis- (4-hydroxybenzyl) -benzene, 1,4-bis- (4-hydroxybenzyl) -tetramethylbenzene, 1,4-bis-
(4-hydroxybenzyl) -tetraethylbenzene,
1,4-bis- (p-hydroxycumyl) -benzene, 1,3
-Bis- (p-hydroxycumyl) -benzene and the like.

Other polynuclear polyhydric phenols (A-2) include, for example, initial condensation products of phenols and carbonyl compounds (eg, phenol resin initial condensation products, condensation reaction products of phenol and acrolein, phenols). And glyoxal condensation reaction products, phenol and pentanediallyl condensation reaction products, resorcinol and acetone condensation reaction products, xylene-phenol-formalin initial condensation products), condensation products of phenols and polychloromethylated aromatic compounds (Example: a condensation product of phenol and bischloromethylxylene) and the like.

Thus, here, the polyhydroxyl compound B means the polyhydric phenol A having at least one aromatic nucleus and the alkylene oxide in the presence of a catalyst for promoting the reaction between the OH group and the epoxy group. It is linked to the phenol residue by an ether bond obtained by reaction-
ROH (where R is an alkylene oxide-derived alkylene group) or (and)-(RO) nH (where R is an alkylene oxide-derived alkylene group and one polyoxyalkylene chain contains different alkylene groups) Also, n is a compound having an atomic group of 2 or an integer of 2 or more, which represents the number of polymerization of the oxyalkylene group. In this case, the ratio of the polyhydric phenol A and the alkylene oxide is 1: 1 (mol: mol) or more, but the ratio of the alkylene oxide to the OH group of the polyhydric phenol A is preferably 1: 1 to 10. , Preferably 1: 1 to 3 (equivalent: equivalent).

Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, and the like. Those which generate a side chain when they react with the polyhydric phenol A to form an ether bond are particularly preferable. As propylene oxide, 1,
There are 2-butylene oxide and 2,3-butylene oxide, and propylene oxide is particularly preferable.

A particularly preferred group of such polyhydroxyl compounds are those of the general formula (Wherein Y ′, Y ₁ , m, z and R ₁ are the same as those in the above formula (1-1), R is an alkylene group having 2 to 4 carbon atoms, and n ₁ and n ₂ are 1 to 3; Which is the value of).

Yet another preferred group of such polyhydroxyl compounds is the general formula (In the formula, R ₁ , R ₂ and R ₃ are the same as those in the formula (1-2), R is an alkylene group having 2 to 4 carbon atoms, and n ₁ and n ₂ are 1
Is a polyhydroxyl compound represented by

Further, the epoxy resin (I-2) having an average of more than one substituted or unsubstituted glycidyl ester group in the molecule is:
There is a polyglycidyl ester of an aliphatic polycarboxylic acid or an aromatic polycarboxylic acid, and for example, an epoxy resin obtained by polymerizing glycidyl methacrylate synthesized from epihalohydrin E represented by the following general formula (4) and methacrylic acid. Is also included.

In addition, an epoxy resin (1--epoxy group having an average of more than one N-substituted or unsubstituted 1,2-epoxypropyl group in the molecule (1-
Examples of 3) include epoxy resins obtained from an aromatic amine such as aniline or aniline having a nuclear alkyl substituent and an epoxy E represented by the following general formula (4), an aromatic amine such as aniline and formaldehyde. Examples thereof include an epoxy resin obtained from a condensate and epihalohydrin E, an epoxy resin obtained from an initial condensate of an aromatic amine such as aniline, a phenol such as phenol, and formaldehyde, and epihalohydrin E.

Then, the polyglycidyl ether (I-1-3) of the polyhydric alcohol C having one or more alicyclic nuclei means, for example, the polyhydric alcohol C having at least one alicyclic nucleus and epihalohydrin. An epoxy resin containing a polyglycidyl ether as a main reaction product, which is obtained by reacting E with a basic catalyst or a basic compound such as sodium hydroxide in the presence of a reaction amount of a basic compound, at least 1
A polyhalohydrin ether obtained by reacting a polyhydric alcohol C having one alicyclic nucleus with an epihalohydrin E by a conventional method in the presence of a catalytic amount of an acidic catalyst such as boron trifluoride and sodium hydroxide. An epoxy resin obtained by reacting with a basic compound or a polyhydric alcohol C having at least one alicyclic nucleus and epihalohydrin E are reacted by a conventional method in the presence of a catalytic amount of a basic catalyst such as triethylamine. An epoxy resin obtained by reacting the resulting polyhalohydrin ether with a basic compound such as sodium hydroxide.

Similarly, the polyglycidyl ether compound (I-1-4) is, for example, a polyhydroxyl group derived from an addition reaction of a polyhydric alcohol C having at least one alicyclic nucleus and an alkylene oxide having 2 to 4 carbon atoms. Compound D and epihalohydrin E are obtained by reacting polyhalohydrin ether obtained by reacting a basic compound such as sodium hydroxide with a polyhalohydrin ether obtained by a conventional method in the presence of a catalytic amount of an acidic catalyst such as boron trifluoride. An epoxy resin containing a polyglycidyl ether as a main reaction product such as
Of these, preferred are polyglycidyl ethers of polyhydric alcohols having one or more alicyclic nuclei and polyhydric alcohols having one or more alicyclic nuclei and 2 to 4 carbon atoms. And polyglycidyl ethers of alcoholic polyhydroxyl compounds derived from the addition reaction of the above with alkylene oxide.

Furthermore, the polyglycidyl ether compound (I-1-3) is an epoxy resin obtained by using a polyhydric phenol having at least one aromatic nucleus instead of the above polyhydric alcohol C, and then hydrogenating the aromatic nucleus. It can also be obtained as a ring nucleus. Examples of the catalyst that can be used in this case include catalysts in which rhodium or ruthenium is held on a carrier as described in JP-B-42-7788.

The polyhydric alcohol C having at least one alicyclic nucleus has a mononuclear polyhydric alcohol (C-1) having one alicyclic nucleus and two or more alicyclic nuclei. There is a polynuclear polyhydric alcohol (C-2).

Preferred examples of the polynuclear polyhydric alcohol (C-1) include the general formula HO- (R ₂ ) fA- (R ₃ ) g-OH (2) (wherein A is a cyclohexane residue and is a methyl group, n- Alkyl group such as propyl group, n-butyl group, n-hexyl group, n-octyl group, preferably an alkyl group having up to 4 carbon atoms or a halogen atom, that is, a chlorine atom, a bromine atom, a fluorine atom or a methoxy group, Methoxymethyl group, ethoxy group, ethoxyethyl group, n-butoxy group,
Maximum of 4 alkoxy groups such as amyloxy group
It may or may not be substituted with an alkoxy group having carbon atoms, but from the viewpoint of heat resistance, halogen substitution or unsubstituted is preferable.

R ₂ and R ₃ may be the same or different, and include, for example, methyl group, n-propyl group, n-butyl group, n-hexyl group,
An alkyl group such as n-octyl group is preferably an alkyl group having a maximum of 6 carbon atoms, and f and g are 0 or 1, but preferably 0). Nuclear polyhydric alcohols, for example, substituted or unsubstituted cyclohexanediols such as 1,4-cyclohexanediol, 2-chloro-1,4-cyclohexanediol, 1,3-cyclohexanediol, and 2-methyl-1,4-cyclohexanediol. And 1,4-dihydroxymethylcyclohexane, 2-chloro-1,4-dihydroxymethylcyclohexane, 1,3-dihydroxymethylcyclohexane, 1,4-dihydroxyethylcyclohexane, 1,3-dihydroxyethylcyclohexane, 1,4 −
There are substituted or unsubstituted dihydroxyalkylcyclohexanes such as dihydroxypropylcyclohexane and 1,4-dihydroxybutylcyclohexane.

Further, as mononuclear polyhydric alcohol having one other alicyclic residue, 1,3-cyclopentanediol, 1,3-cycloheptanediol, 1,4-cycloheptanediol,
1,3-cycloheptanediol, 1,5-perhydronaphthalenediol, 1,3-dihydroxy-2,2,4,4-tetramethylcyclobutane, 2,6-dihydroxy-decahydronaphthalene, 2,7-dihydroxy Other substituted or unsubstituted cycloalkyl polyols such as decahydronaphthalene, 1,5-dihydroxy-decahydronaphthalene and
1,3-dihydroxymethylcyclopentane, 1,4-dihydroxymethylcycloheptane, 2,6-bis (hydroxymethyl) -decahydronaphthalene, 2,7-bis (hydroxymethyl) -decahydronaphthalene, 1,5- Bis (hydroxymethyl) -decahydronaphthalene, 1,4-bis (bidoxymethyl) -decahydronaphthalene, 1,4-
Other substituted or unsubstituted polyhydroxyalkylcycloalkanes such as bis (hydroxymethyl) -bicyclo [2.2.2] octane, dimethylroll tricyclodecane are included.

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

Further, examples of the polynuclear polyhydric alcohol (C-2), the general _{formula: HO- (R 2) f- (} A 1) k - _{[(R 1) j- (A 2} ) L ] i-(R ₃ ) gO
H (3) (wherein A ₁ and A ₂ are mono- or polycyclic divalent alicyclic hydrocarbon residues, such as methyl group, n-propyl group, n-butyl group, n
-Alkyl group such as hexyl group and n-octyl group, preferably an alkyl group having up to 4 carbon atoms or a halogen atom, that is, a base atom, a bromine atom or a fluorine atom, a methoxy group, a methoxymethyl group, an ethoxy group, ethoxyethyl. Group, an n-butoxy group, an amyloxy group, an alkoxy group, preferably an alkoxy group having a maximum of 4 carbon atoms, and the like, which may or may not be substituted, but from the viewpoint of heat resistance, a halogen atom. Substituted or unsubstituted is preferred.

K and 1 are 0 or 1, but k and l are never 0.

R ₁ has the same definition as in the general formula (1), but from the viewpoint of heat resistance and the like, it is preferable that R ₁ is a methylene group, an ethylene group, or an isopropylene group. j is 0 or 1.

R ₂ and R ₃ may be the same or different, and include, for example, methyl group, n-propyl group, n-butyl group, n-hexyl group,
Alkyl group such as n-octyl group is preferably an alkyl group having up to 6 hydrocarbons, and f and g are 0 or 1, but preferably 0. i is a number of 0 or more, preferably 0 or 1. Such a polynuclear polyhydric alcohol (C-2), particularly preferred is the general formula: HO-A _1- (R ₁ ) jA ₂ -OH ( 3-1) A polynuclear dihydric alcohol represented by the formula (A ₁ , A ₂ , R ₁ and j are the same as those defined in the general formula (3)).

Preferred examples of such polynuclear dihydric alcohol include, for example, 4,
4'-bicyclohexanediol Substituted or unsubstituted bicycloalkanediol such as 3,3'-bicyclohexanediol and octachloro-4,4'-bicyclohexanediol, or 2,2-bis- (4-hydroxycyclohexyl) propane , 2,4'-dihydroxydicyclohexylmethane, bis- (2-hydroxycyclohexyl) methane, bis- (4-hydroxycyclohexyl) methane, bis (4-hydroxy-2,6-dimethyl-3-methoxycyclohexyl) methane, 1 1,1-bis- (4-hydroxycyclohexyl) ethane, 1,1-bis- (4-hydroxycyclohexyl) propane, 1,1-bis- (4-hydroxycyclohexyl) butane, 1,1-bis (hydroxycyclohexyl) Pentane, 2,2-bis (4-hydroxycyclohexyl) butane, 2,2-bis (4-hydroxyhexyl) pentane, 3,3-bis (4-hydroxycyclohexyl) pentane, 2,2-bis (4-hydroxycyclohexyl) heptane, bis (4-hydroxycyclohexyl) phenylmethane, bis (4-hydroxycyclohexyl) ) Cyclohexylmethane, 1,2-bis (4-hydroxycyclohexyl) -1,2-bis (phenyl) propane, 2,2-bis (4-hydroxycyclohexyl) -1-phenylpropane, 2,2-bis (4 -Hydroxy-3-methylcyclohexyl) propane, 2,2
-Bis (4-hydroxy-2-methylcyclobutanehexyl) propane, 1,2-bis (4-hydroxycyclohexyl) ethane, 1,1-bis (4-hydroxy-2-chlorocyclohexyl) ethane, 1,1-bis (3,5-dimethyl-4-hydroxycyclohexyl) ethane, 1,3-bis (3-methyl-4-hydroxycyclohexyl) propane, 2,2-bis (3,5-dichloro-4-hydroxycyclohexyl) propane, 2,2-bis (3-phenyl-4)
-Hydroxycyclohexyl) propane, 2,2-bis (3-isopropyl-4-hydroxycyclohexyl)
Bis (hydroxycycloalkyl) alkane such as propane, 2,2-bis (2-isopropyl-4-hydroxycyclohexyl) propane, 2,2-bis (4-hydroxyperhydronaphthyl) propane or 4,4'-dihydroxy Dihydroxy chloroalkane such as dicyclohexane, 2,2'-dihydroxybicyclohexane, 2,4-dihydroxybicyclohexane or bis (4-hydroxycyclohexyl) sulfone, 2,4'-dihydroxycyclohexyl sulfone, chloro-2,4- Dihydroxydicyclohexyl sulfone, 5-chloro-4,4'-dihydroxydicyclohexyl sulfone, 3'-chloro-
Di (hydroxycycloalkyl) sulfone such as 4,4'-dihydroxydicyclohexyl sulfone or bis (4-hydroxycyclohexyl) ether, 4,3'-
(Or 4,2'- or 2,2'- or 2,3'-dihydroxy-
Dicyclohexyl) ether, 4,4'-dihydroxy-
2,6-Dimethyldicyclohexyl ether, bis (4-
Hydroxy-3-isobutylcyclohexyl) ether, bis (4-hydroxy-3-isopropylcyclohexyl) ether, bis (4-hydroxy-3-chlorocyclohexyl) ether, bis (4-hydroxy-3)
-Fluorocyclohexyl) ether, bis (4-hydroxy-3-bromocyclohexyl) ether, bis (4-hydroxyperhydronaphthyl) ether, bis (4-hydroxy-3-chloroperhydronaphthyl) ether, bis (2- Hydroxy (bicyclohexyl) ether, 4,4'-dihydroxy-2,6-dimethoxy-dicyclohexyl ether, di (hydroxycycloalkyl) ether such as 4,4'-dihydroxy-2,5-diethoxyylcyclohexyl ether 1,1-bis (4-hydroxycyclohexyl) -2-phenylethane, 1,3,3-trimethyl-1- (4-hydroxycyclohexyl) -6-hydroxyintan, 2,4-bis (p
-Hydroxycyclohexyl) -4-methylpentane is also suitable.

Furthermore, another preferable group of such polynuclear dihydric alcohols is represented by the general formula: HO-A _1- (R ₁ ) jA _2- (R ₁ ) jA ₂ -OH (3-2) (wherein A ₁ , A ₂ , R ₁ and j are the same as defined in the above general formula (3), and are represented by two R ₁ , two j, and two A ₂ may be different from each other. And, for example, 1,4-bis (4-
Hydroxycyclohexylmethyl) cyclohexane, 1,
4-bis (4-hydroxycyclohexylmethyl) tetramethylcyclohexane, 1,4-bis (4-hydroxycyclohexylmethyl) tetraethylcyclohexane,
Examples include 1,4-bis (p-hydroxycyclohexylisopropyl) cyclohexane and 1,3-bis (p-hydroxycyclohexylisopropyl) cyclohexane.

A further preferred group of such polynuclear dihydric alcohols is represented by the general formula: HO-R ₂ -A _1- (R ₁ ) jA ₂ -R ₃ -OH (3-3) (wherein A ₁ , A ₂ ,, R ₁ , R ₂ , R ₃ , j are the same as defined in the above general formula (3)), and are, for example, 4,4'-
A substituted or unsubstituted dihydroxyalkylbicycloalkane such as dihydroxymethylbicyclohexane, and 1,
2-bis (4-hydroxymethylcyclohexyl) ethane, 2,2-bis (4-hydroxymethylcyclohexyl) propane, 2,3-bis (4-hydroxymethylcyclohexyl) butane, 2,3-dimethyl-2,3- Bis (4-
Included are substituted or unsubstituted bis (hydroxyalkylcycloalkyl) alkanes such as hydroxymethylcyclohexyl) butane.

Thus, the polyhydroxy compound D here means the presence of a catalyst for promoting the reaction of the polyhydric alcohol C having at least one alicyclic nucleus and the alkyl oxide with the OH group and the epoxy group. Is bonded to the alicyclic residue by an ether bond obtained by reacting with. ‐ROH
(Where R is an alkylene group derived from alkylene oxide) or (and)-(RO) nH (where R is an alkylene group derived from alkylene oxide, and one polyoxyalkylene chain may contain different alkylene groups. N is a compound having an atomic group of 2 or an integer of 2 or more, which indicates the number of polymerization of the oxyalkylene group. In this case, the ratio of the polyhydric alcohol C 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 alcohol C is 1:10 to 10: 1. And particularly preferably 1: 1 to 3 (equivalent:
Equivalent).

Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, etc., and when these react with the polyhydric alcohol C to form an ether bond, those which generate a side chain are particularly preferable. Examples include propylene oxide, 1,2-butylene oxide, and 2,3-butylene oxide, and propylene oxide is particularly preferable.

A particularly preferred group of such polyhydroxyl compounds is represented by the general formula: H (OR) n ₁ OA _1- (R ₁ ) jA ₂ -O (RO) n ₂ H (wherein A ₁ , A ₂ , R ₁ and j are the same as those in the general formula (3-1), R is an alkylene group having 2 to 4 carbon atoms, and n ₁ and n ₂ are values of 1 to 3) It is a hydroxyl compound.

Yet another such group of preferred polyhydroxyl compounds is the general formula: H (OR) n ₁ OA _1- (R ₁ ) jA _2- (R ₁ ) jA ₂ -O (RO) n ₂ H (wherein A ₁ , A ₂ , R ₁ and j are the same as those in the general formula (3-2), R is an alkylene group having 2 to 4 carbon atoms, and n ₁ and n ₂ are 1 to 3; Is a value) of the polyhydroxyl compound.

Among these mononuclear or polynuclear polyhydric alcohols C, particularly preferable one is a cyclohexane ring having 1 as alicyclic residue.
Or, it has two, and among them, dihydroxymethylcyclohexane and 2,2-bis (4-hydroxycyclohexyl) propane are preferable.

In addition, here, epihalohydrin E has the general formula: (Wherein Z is a hydrogen atom, a methyl group, an ethyl group and X'is a halogen atom). Examples of such epihalohydrin E include, for example, epichlorohydrin, epibromhydrin, 1,2-epoxy. 2-Methyl-3-chloropropane, 1,2-epoxy-2-ethyl-3-chloropropane and the like can be mentioned.

The acidic catalyst that promotes the reaction of the epihalohydrin E with the polyhydric phenol A, the polyhydroxyl compound B, the polyhydric alcohol C or the polyhydroxyl compound D includes
Lewis acids such as boron trifluoride, stannic chloride, zinc chloride and ferric chloride, derivatives showing these activities (eg boron trifluoride-ether complex compound) or mixtures thereof can be used. .

Similarly, as the chlorinating catalyst for promoting the reaction of epihalohydrin E with polyhydric phenol A, polyhydroxyl compound B, polyhydric alcohol C or polyhydroxyl compound D, alkali metal hydroxide (eg sodium hydroxide), alkali Metal alcoholates (eg sodium ethylate), tertiary ammine compounds (eg triethylamine, triethanolamine), quaternary ammonium compounds (eg tetramethylammonium bromide) or mixtures thereof can be used, but Alkali metal hydroxide (for example, as a basic compound which can form a glycidyl ether at the same time as the above reaction, or a halohydrin ether formed as a result of the reaction can be closed by a dehydrohalogenation reaction to form a glycidyl ether (eg: Sodium hydroxide Helium), alkali metal aluminates (e.g. sodium aluminate) is used conveniently.

However, it goes without saying that these catalysts or basic compounds can be used as they are or as a suitable inorganic or / and organic solvent liquid.

An acidic catalyst has a large catalytic effect for promoting the reaction of epihalohydrin E with polyhydric phenol A, polyhydroxyl compound B, polyhydric alcohol C or polyhydroxyl compound D.

Further, a polyglycidyl ether compound obtained by reacting a mixture of the above polyhydric alcohols with epihalohydrin can also be used in the composition of the present invention.

Examples of the epoxidized polyunsaturated compound (I-4) include epoxidized polybutadiene (so-called oxylone), vinylcyclohexene dioxide, limonene dioxide, dicyclopentanediene oxide,
Bis (3,4-epoxycyclohexylmethyl) phthalate, diethylene glycol-bis (3,4-epoxy-cyclohexenecarboxylate), 3,4-epoxy-6
-Methyl-cyclohexylmethyl-3,4-epoxy-6
-Methylcyclohexanecarboxylate, 3,4-epoxy-hexahydrobenzal-3,4-epoxy-cyclohexane-1,1-dimethanol and ethylene glycol-bis (3,4-epoxytetrahydro-dicyclopentadiene-8- Il) ether can be mentioned.

In addition, conventionally known adjacent epoxy group-containing epoxy resins such as various epoxy resins described in "Manufacturing and Application of Epoxy Resin" (edited by Hiroshi Kakiuchi) are used.

Preferred as the urethane bond-containing compound (-a) used in the present invention for the production of the flexibility-imparting agent for epoxy resin is polyether polyol, polyester polyol, or a mixture thereof and a polyisocyanate compound, which are usually used as NCO. It is an isocyanate group having 1 to 10% by weight and an average molecular weight of 2740 to 3720, which is obtained by reacting in the same manner as in the production method of the contained urethane prepolymer.

Preferred examples of the above polyether polyols include, for example, the general formula R [(OR ₁ ) nOH] p (wherein R is a polyhydric alcohol residue; (OR ₁ ) n is an oxy group having an alkylene group having 2 to 4 carbon atoms. Polyoxyalkylene chain consisting of alkylene group; n is a number corresponding to the degree of polymerization of the oxyalkylene group and having a molecular weight of 100 to 4,500; p is preferably 2 to 4) is there.

Preferred examples of the polyhydric alcohol corresponding to the above general formula include, for example, aliphatic dihydric alcohols (eg, ethylene glycol, propylene glycol, 1,4-butylene glycol, neopentane glycol), trihydric alcohols (eg: glycerin). , Trioxyisobutane, 1,2,3-butanetriol, 1,2,3-pentanetriol, 2-methyl-1,2,3-propanetriol, 2-methyl-2,3,4
-Butanetriol, 2-ethyl-1,2,3-butanetriol, 2,3,4-pentanetriol, 2,3,4-hexanetriol, 4-propyl-3,4,5-heptanetriol, 2, 4-dimethyl-2,3,4-pentanetriol, pentamethylglycerin, pentaglycerin, 1,2,4-butanetriol, 1,2,4-pentanetriol, trimethylolpropane, etc., tetrahydric alcohol (e.g .: Erythritol, pentaerythritol, 1,2,3,4-pentanetetrol, 2,3,4,5-hexanetetrol, 1,2,3,5-pentanetetrol, 1,3,4,5- Hexanetetrol, etc.), pentahydric alcohol (eg, Adnit, arabite, xylit, etc.), hexavalent alcohol (eg, sorbit, mannitol, idit, etc.) and the like.

The polyhydric alcohol is preferably a dihydric to tetrahydric alcohol, and propylene glycol and glycerin are particularly preferable.

Further, the polyether polyol represented by the above general formula,
It can be produced by adding an alkylene oxide having 2 to 4 carbon atoms to such a polyhydric alcohol by a conventional method so as to have a desired molecular weight.

Further, as the alkylene oxide having 2 to 4 carbon atoms,
Examples thereof include ethylene oxide, propylene oxide and butylene oxide, and it is particularly preferable to use propylene oxide.

Examples of the above polyester polyols include conventionally known polyesters produced from polycarboxylic acids and polyhydric alcohols or polyesters obtained from lactams.

Examples of such polycarboxylic acid include benzenetricarboxylic acid, adipic acid, succinic acid, speric acid, sebacic acid, oxalic acid, methyladipic acid, glutaric acid, pimelic acid, azelaic acid, phthalic acid, terephthalic acid, isophthalic acid, thiodicarboxylic acid. Propionic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid or any suitable carboxylic acid similar thereto can be used.

Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, 1,4-butanediol, 1,3
-Butanediol, 1,5-pentanediol, 1,6-hexanediol, bis (hydroxymethylchlorohexane), diethylene glycol, 2,2-dimethylpropylene glycol, 1,3,6-hexanetriol, trimethylolpropane, penta Erythritol, sorbitol, glycerin or any suitable polyhydric alcohol similar thereto can be used.

Urethane bond-containing compound (-a) used in the present invention
Can be obtained, for example, by reacting the above-mentioned polyether polyol, polyester polyol, a mixture thereof, or a mixture thereof with an OH group-containing glyceride such as castor oil and polyisocyanate.

In addition, the polyisocyanate compound here has a general formula (Where ◯ is a benzene ring or naphthalene ring, -NCO is a nucleus-substituted isocyanate group, Z is a nucleus-substituted halogen atom or an alkyl or alkoxyl group having 3 or less carbon atoms,
n is a diisocyanate represented by 0, 1 or 2 (for example,
2,4-toluylene diisocyanate, 2,6-toluylene diisocyanate, 1,4-naphthylene diisocyanate,
1,5-naphthylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate,
1-isopropylbenzol-2,4-diisocyanate): general formula (Where ○ is benzene ring or naphthalene ring,-(C
H ₂ ) mNCO is a nucleus-substituted alkylene isocyanate group, Z is a nucleus-substituted halogen atom or an alkyl or alkoxyl group having 3 or less carbon atoms, m is 1 or 2, and n is 1 or 2). , Ω'-diisocyanate-1,2-dimethylbenzol, ω, ω'-diisocyanate-1,3-dimethylbenzol): general formula (Where A is -CH ₂ -or An alkylene group having 3 or more carbon atoms, such as ◯, a benzene ring or a naphthalene ring, Z is a halogen atom substituted with a nucleus, or an alkyl or alkoxy group having 3 or less carbon atoms, and n is a diisocyanate represented by 0, 1 or 2 (eg, : 4,4'-diphenylmethane diisocyanate, 2,2'-dimethyldiphenylmethane-4,4'-diisocyanate, diphenyldimethylmethane-4,4'-diisocyanate, 3,3'-dichlorodiphenyldimethylmethane-4,4 ' -Diisocyanate), general formula (Wherein Z is a nuclear-substituted halogen atom or an alkyl or alkoxy group having 3 or less carbon atoms, m is 0 or 1, n is 0,
1 or 2) diisocyanate (eg, biphenyl-2,4'-diisocyanate, biphenyl-4,4'-diisocyanate, 3,3'-dimethylbiphenyl-4,4'-
Diisocyanate, 3,3'-dimethoxybiphenyl-4,
4'-diisocyanate), diphenylsulfone-4,4 '
-Diisocyanates, diisocyanates such as those obtained by hydrogenating the aromatic rings contained in said isocyanates (eg dichlorohexane-4,4'-diisocyanate, ω, ω'-
Diisocyanate-1,2-dimethylbenzene, ω, ω ′
-Diisocyanate-1,3-dimethylbenzene), a diisocyanate containing substituted urea groups obtained by the reaction of 2 mol of diisocyanate and 1 mol of water (eg 1 mol of water and 2 mol of 2,4-toluylene diisocyanate) Urea diisocyanate obtained by the reaction of), uretdione diisocyanate obtained by polymerizing two molecules of aromatic diisocyanate by a known method, propane-1,2-diisocyanate, 2,3-dimethylbutane-2,3-diisocyanate, 2-Methylpentane-2,4-diisocyanate, octane-3,6-diisocyanate, 3,3-dinitropentane-1,5-diisocyanate, octane-1,6-diisocyanate, hexamethylene diisocyanate and the like can be mentioned.

The urethane bond-containing compound (-a) obtained from such an isocyanate compound and a polyhydroxyl compound such as the above polyether polyol or polyester polyol can be obtained by a usual method. When carrying out the urethane bond-containing compound formation reaction, the reaction temperature is usually 40 to 140 ° C, preferably 60 to 120 ° C. In carrying out the urethane bond-containing compound forming reaction, a known urethane polymerization catalyst for promoting the reaction, for example, dibutyltin dilaurate, stannous octoate, organometallic compounds such as stannas octoate, triethylenediamine, triethylamine, 1, It is also possible to use a tertiary amine compound such as 8-diazabicyclo [5.4.0] undecene-7.

Examples of the compound (-b) having a monovalent phenolic hydroxyl group that causes a block reaction with the NCO group-containing urethane prepolymer (-a) include phenol, clay sol (metacresol, orthocresol, para-cresol and mixtures thereof), xylenol. , Octylphenol, nonylphenol, dinonylphenol, para-tert-butylphenol, sec-butylphenol, and other alkylphenols, styrenated phenols, and the like, and a mixture of two or more of these phenols is also included.

The blocking reaction of isocyanate / phenols is carried out by a known reaction method. The reaction temperature is preferably 50 ° C to 150 ° C, more preferably 70 ° C to 120 ° C, and the reaction time is 1
It is preferably carried out in about 7 hours. The equivalent ratio is NCO / phenolic OH = 1 / 1.0 to 1.5.

The blocking agent can be added and reacted at any stage of the above reaction to obtain a blocked isocyanate compound.

As a method of addition, it is possible to add at the end of a predetermined polymerization, to add at the beginning of the polymerization, or to add a part at the beginning of the polymerization and add the rest at the end of the polymerization.
A method of adding at the end of the polymerization is preferred. During the reaction, a known urethane polymerization catalyst may be added to accelerate the reaction.

Preferable examples of the active amino compound curing agent used in the present invention include aliphatic polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, dipropylenetriamine, dimethylaminopropylamine, diethylaminopropylamine, cyclohexylaminopropylamine, and monoamines. Ethanolamine,
Aliphatic hydroxymonoamines such as diethanolamine, propanolamine and N-methylethanolamine; aliphatic hydroxypolyamines such as aminoethylethanolamine, monohydroxyethyldiethylenetriamine, bishydroxyethyldiethylenetriamine, N (2-hydroxypropyl) ethylenediamine; dimers A polyamide obtained by condensation of an acid and a diamine (for example, ethylenediamine); an epoxy compound (for example, ethylene oxide, which has an average of less than two 1,2-epoxy groups in a stoichiometrically deficient amount of any of them and the like). Propylene oxide, epichlorohydrin, styrene oxide, methyl glycidyl ether, phenyl glycidyl ether, glycidyl methacrylate, etc.) Called modified aliphatic amine curing agent; aniline, toluidine, ethylaniline, xylidine, benzidine, 4,4'-diaminodiphenylmethane,
2,4,6-Tri (dimethylaminomethyl) phenol, 2,2
-Bis (4aminophenyl) propane, 4,4'-dianodiphenyl ether, 4,4'-dianodiphenyl sulfone, 4,4'-diaminobenzophenone, 2,2'-dimethyl-4,4'-diaminodiphenylmethane , 2,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, aromatic amines such as fragrance Initial condensation product of a group amine with an aldehyde or a reactive derivative of an aldehyde (for example, an aliphatic lower aldehyde such as formaldehyde, paraformaldehyde, acetaldehyde, chloral, etc., particularly formaldehyde or a reactive derivative thereof), such an aromatic amine Phenols (eg phenol, cresol, xylenol,
Initial condensation of (ethylphenol, chlorophenol, anisole) with an aldehyde or a reactive derivative of aldehyde as described above, or a stoichiometrically deficient amount of one or more of these and 1,2-epoxy having an average of less than 2 in the molecule Examples thereof include amine adducts (modified amines) obtained by reaction with an epoxy compound having a group.

Other amino group-containing curing agents contained in the active organic amine compound curing agent include aliphatic amines having a cyclic structure such as piperazine, N-aminoethylpiperazine and triethylenediamine; metaphenylenediamine,
Meta-xylenediamine, para-xylenediamine, p, p ′
Aromatic primary amines such as diaminodiphenylmethane, diaminophenylsulfone; benzyldimethylamine,
2-methyl-dimethylamine, tri (dimethylaminomethyl) such aromatic tertiary amine _{benzene, BF 3 · C 2 H 5} NH 2,
Examples thereof include BF ₃ · piperazine, trialkanolamine borate; amine titanate; cyanoethylated polyamines; melamine resin precondensate and amino resin precondensate.

Other trimethylhexamethylenediamine, Isophorone diamine Can also be used.

Particularly preferred active organic amine compound curing agents are those having one or more cycloaliphatic rings, examples of which are 1-cyclohexylamino-3-aminopropane, 1,4
-Diaminocyclohexane, 1,3-diaminocyclopentane, di- (aminocyclohexyl) methane, di- (aminocyclohexyl) sulfone, 1,3-di- (aminocyclohexyl) propane, 4-isopropyl-1,2-diaminocyclohexane , 2,4-diamino-cyclohexane, N, N'-diethyl-1,4-diaminocyclohexane,
There are 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane and 3-aminomethyl-3,3,5-trimethyl-cyclohexylamine. Diprimary cycloaliphatic amines are particularly suitable for the mixtures according to the invention.

More preferable other amine curing agent is 3,9-bis (3-aminopropyl) -2,4,8,10-tetraspiro (5.
5] Undecane (ATU) (ATU is a diamine with a unique structure containing a spiro ring in the molecule, melting point 47-48 ℃, active hydrogen equivalent
Although it is 68.6, the commercial product is a trademark of Epomate, which is variously modified to be a liquid curing agent.

Derivatives of the above compounds, epoxy adducts, acrylonitrile adducts, diamines having a hydantoin ring, (R ₁ and R ₂ are hydrogen or lower alkyl) Di- and triamines having an ether bond in the main chain (the series of diamines include polyoxypropylene chain amines having the following structure, Specifically, there are polyether diamines D-230, D-400, D-2000 of Mitsui Texaco Co., Ltd. and triamine of T-403 below, The number after D- almost indicates the molecular weight. Also, polyoxyethylene chain diamine, ED-600, ED-900, ED-2000
There is also).

The preferable compounding ratio of each component of the composition of the present invention is as follows.

Epoxy resin / epoxy resin flexibility imparting agent = 90 to 10
/ 10 to 90 (weight ratio), preferably / = 20 to 70/80 to 30
(Weight ratio), compounding ratio of curing agent is + / = 100/60
To 4 (weight ratio), preferably + / = 100/30 to 6
(Weight ratio).

In addition to these essential ingredients, the composition according to the invention comprises reactive diluents, non-reactive diluents and extenders, fillers and / or reinforcing agents, pigments, solvents, plasticizers, leveling agents, thixotropic agents. , A flame-retardant substance, a release agent, and other conventional modifiers may be contained. The following are examples of suitable diluents, extenders, reinforcing agents, fillers and pigments that may be used in the composition. Monoglycidyl ether, DP
Bituminous materials such as O, DBP, xylene resin, benzyl alcohol, tetrahydrofurfuryl alcohol, allorizer, coal tar, bitumen, textile fiber, fibrin, glass fiber, synthetic fiber, asbestos fiber, boron fiber, carbon fiber, cellulose, polyethylene Powders, clays, sands, rocks, quartz powders, mineral silicates such as mica, asbestos powder, ground shale, kaolin, aluminum hydroxide, powdered chalk, gypsum, antimony trioxide, bentonite, silica airgel, lithopone, heavy crystals. Stone, titanium dioxide, talc,
Oxide pigments such as calcium carbonate, carbon black, graphite, iron oxide, or metal powders such as aluminum powder or iron powder.

Suitable solvents for modifying the curable composition include, for example, toluene, xylene, n-propanol, butyl acetate, acetone, methyl ethyl ketone, diacetone, ethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether and ethylene glycol. There is monobutyl ether.

Suitable plasticizers for modifying the curable composition include
Examples are the dibutyl-, dioctyl- and dinonyl esters of phthalic acid, tricresyl phosphate, trixylenyl phosphate and polypropylene glycol.

Leveling agents which may be added when the curable composition is to be used especially for surface protection include, for example, silicone, acetylbutyl cellulose, polyvinyl butyrate, waxes and stearates.

The curable composition may be produced by a known method using a known mixing device (stirring machine, kneader, roller, etc.).

〔Example〕

The present invention is described in detail below with reference to examples, but the present invention is not limited thereto.

Production Example 1 1000 parts of polypropylene glycol (molecular weight: 2000) and 174 parts of toluylene diisocyanate (molecular weight: 174) were reacted in a four-necked flask equipped with a stirrer, a thermometer and a nitrogen inlet tube at 70 ° C for 5 hours. Isocyanate equivalent 1174
(NCO content 3.6%) urethane prepolymer was obtained, followed by addition of 242 parts of nonylphenol (molecular weight: 220) at 70 ° C, 5
Blocked isocyanate compound A in which isocyanate groups have completely disappeared by infrared absorption spectrum after reacting with time
Was obtained (blocked isocyanate equivalent weight 1400).

Production Example 2 1500 parts of polypropylene glycol (molecular weight: 3000) and 250 parts of diphenylmethane diisocyanate (molecular weight: 250) were reacted in the same manner as in Production Example 1 to obtain an isocyanate equivalent of 1750.
A urethane prepolymer (NCO content 2.4%) was obtained, 108 parts of cresol (molecular weight: 108) was further added, and the reaction was carried out in the same manner as in Production Example 1 to obtain a blocked isocyanate compound B (block isocyanate equivalent weight 1860).

Production Example 3 1000 parts of a polyester diol (molecular weight: 2000) obtained from diethylene glycol and adipic acid, 222 parts of isophorone diisocyanate (molecular weight: 222), and 0.1 part of tin octylate were reacted in the same manner as in Production Example 1 to produce an isocyanate equivalent. A 1222 (NCO content 3.4%) urethane prepolymer was obtained, and paratertiary butylphenol (molecular weight: 1
50) 150 parts were reacted at 100 ° C. for 5 hours to obtain a blocked isocyanate compound C in the same manner as in Production Example 1 (block isocyanate equivalent weight 1370).

Example 1 The composition shown in Table 1 was cured and the physical properties before and after outdoor exposure were examined.

The cured products of the products 1-1, 1-2, and 1-3 of the present invention are all 30
It can be said that the performance after Nikkei day is not much different from the initial performance and there is almost no change in the physical property values over time. In comparison, it can be seen that the flexible epoxy / polyamide-based comparative product 1-4 has undergone a remarkable change in the initial physical properties and the physical properties after 30 days, indicating that the curing is progressing.

When the alicyclic amine, Larosin C-260, was used as the curing agent in the above epoxy compounding system, it did not completely cure at room temperature even after 2 days.

Example 2 The composition shown in Table 2 was cured and the physical properties were examined.

Example 3 The composition shown in Table 3 was cured and the physical properties at 25 ° C. and −10 ° C. were examined.

Example 4 The composition shown in Table 4 was cured and the physical properties were examined.

Examples 5 to 8 and Comparative Example 1 The curable compositions shown in Table 5 were cured and measured for adhesion, Erichsen, impact resistance, flex resistance, and water resistance. The results are shown in Table 5.

Examples 9 to 10 and Comparative Example 2 The compositions shown in Table 6 were cured, and hardness, tensile strength and elongation were measured at 25 ° C and 0 ° C, respectively.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hiroshi Suzuki 8-10-9 Higashiohisa, Arakawa-ku, Tokyo ACR Co., Ltd. (72) Inventor Tetsuo Yokokawa 3rd, Kayamotomura-cho, Shinjuku-ku, Tokyo No. 23 within Chow Bond Construction Co., Ltd. (72) Inventor Takeshi Tokuda No. 3-23, Kayamotomura, Shinjuku-ku, Tokyo Within Chow Bond Construction Co., Ltd. (56) References Japanese Patent Laid-Open No. 50-127999 (JP, A) Kai 51-145598 (JP, A) JP 62-195014 (JP, A)

Claims (1)

[Claims] 1. An epoxy resin having an average of more than one adjacent epoxy groups in the molecule as an essential constituent, a polyhydroxy compound and an isocyanate group-containing 1 to 10% by weight, which is obtained from an excess polyisocyanate compound. A urethane bond-containing compound (-a) having an average molecular weight of 2740 to 3720 is reacted with a compound (-b) having a monovalent phenolic hydroxyl group at an NCO / phenolic OH equivalent ratio of 1 / 1.0 to 1.5,
The isocyanate group of the compound (-a) is replaced by the compound (-
b) A flexibility-imparting agent for an epoxy resin consisting of a blocked isocyanate compound obtained by masking with a hydroxyl group, and an active organic amino compound (excluding 1,3-bis (aminomethyl) cyclohexane) curing agent. Curable composition characterized.