JPH0674319B2 - Curable composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a curable composition, specifically a curable epoxy resin composition.

Further, the present invention relates to a curable epoxy resin composition having excellent mechanical strength and adhesiveness, a low water absorption rate, and a flexible, particularly rubber-like, cured product.

Furthermore, the present invention relates to a curable epoxy resin composition having rubber elasticity even at low temperatures.

Furthermore, the present invention has good compatibility with an epoxy resin,
The present invention relates to a novel curing agent capable of improving undesired phenomena such as blooming, brushing, and sweating during curing and imparting excellent adhesiveness to an epoxy resin even under severe conditions such as high humidity or water.

[Conventional technology and problems]

As a reactive curing agent for curing a conventional polyepoxide composition, an aliphatic polyamine, a polyamide, an aromatic polyamine, a cycloaliphatic polyamine, an amino-substituted aliphatic alcohol and phenol, a low molecular weight epoxide containing oxirane oxygen, and Adducts with polyamines are used. However, the above-described conventionally known curing agents have various drawbacks.

For example, the aliphatic amines alone are toxic and easily absorb moisture and carbon dioxide in the air, so the coating becomes white during curing, sweating (sweat phenomenon) occurs, and "repelling" Or there is an undesirable phenomenon,
Since the obtained cured product is not flexible and hard and brittle, the application is considerably controlled.

Further, addition of epoxide to polyamine, that is, amine adduct was able to improve the above-mentioned drawbacks of the aliphatic amine to some extent, but it is still difficult to obtain satisfactory results in terms of adhesiveness and the like.

On the other hand, polyamides have some drawbacks that should be improved and the adhesiveness should be observed, but the characteristics are significantly deteriorated in the presence of water, and the curing characteristics at -10 ° C or lower are insufficient.
Since the obtained cured product also has poor water resistance and chemical resistance, it is unsuitable for outdoor work and corrosion-resistant lining in the winter and rainy seasons, and like polyamines, it is limited in terms of use.

In addition, when a conventional known curing agent is used, even if a flexible resin is added to the epoxy resin as the cured resin, the cured product loses its flexibility at low temperatures and the hardness increases with time. However, it loses flexibility and elasticity, and practically has flexibility even at low temperatures,
Moreover, it has been impossible to obtain an epoxy resin having flexibility and elasticity after long-term outdoor exposure.

A method of introducing a urethane component by using a long-chain amine to improve such a defect, or by adducting a ethane-modified epoxy resin containing a urethane component to an amine-based hardener as in Japanese Patent Publication No. 50-23080. However, none of them could retain the flexibility at low temperature and the flexibility when used outdoors for a long time.

In addition, conventional direct contact of amine / isocyanate is extremely instantaneous, the control is extremely difficult and gelation occurs easily. Therefore, a large amount of solvent is required. Commercialization of the agent was extremely difficult commercially.

Therefore, it has been desired to develop an improved new epoxy resin curing agent that does not have such drawbacks.

Therefore, an object of the present invention is to provide an epoxy resin which does not have the above-mentioned drawbacks, that is, has good adhesiveness even under severe conditions such as high temperature or water, and has excellent flexibility and flexibility at low temperature. The object of the present invention is to provide an epoxy resin curable composition which has the property of maintaining the flexibility and the flexibility of being left outdoors for a long time.

[Means for Solving the Problems] The curable composition for an epoxy resin of the present invention has (a) an epoxy resin having an average of more than one adjacent epoxy groups in the molecule, as an essential component, (B) Urethane prepolymers obtained from a polyhydroxy compound and an excess of polyisocyanate compound having an average of more than one isocyanate group in the molecule of 1 to 10% by weight and an average molecular weight of 600 to 20,000 (b-1 -A) is a compound having a phenolic hydroxyl group (b-1-b), NCO / phenolic hydroxyl group equivalent ratio = 1/1.
A urea-containing active organic compound obtained by reacting a blocked isocyanate compound (B-1) obtained by masking with 0 to 1 / 2.0 with an active organic amino group-containing compound (B-2) in excess of amine. It is an epoxy resin curable composition containing an amine curing agent and free from the above-mentioned drawbacks.

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 epihalohydrin E in the presence of an acidic catalytic amount such as boron trifluoride by a conventional method and a basic substance such as sodium hydroxide. Epoxy resin as obtained by reacting with a compound or polyphenol A having at least one aromatic nucleus and epihalohydrin E as obtained by a conventional method in the presence of a catalytic amount of a basic catalyst such as triethylamine. It is an epoxy resin obtained by reacting a halohydrin 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 boron trifluoride with a basic compound such as sodium hydroxide. An epoxy resin containing such a 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 polyphenols (A-1) include resorcinol, hydroquinone, pyrocatechol, phloroglucinol, 1,5-dihydroxynaphthalene, 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, methoxymethyl 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 alkylene group such as methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, 2-ethyl-hexamethylene group, octamethylene Methylene group, nonamethylene group, decamethylene group or alkylidene group such as ethylidene group, propylidene group, isopropylidene group, isobutylidene group, amylidene group, isoamylidene group, 1-phenylethylidene group or cyclic aliphatic group such as 1,4-cyclohexylene group, 1,3-Cyclohexylene group, cyclohexylidene group, halogenated alkylene group, halogenated alkylidene group, halogenated cycloaliphatic group or alkoxy- and aryloxy-substituted alkylidene group or alkoxy- And aryloxy-substituted A alkylene group or an alkoxy- and aryloxy-substituted cycloaliphatic group such as methoxymethylene group, ethoxymethylene group, ethoxyethylene group, 2-ethoxytrimethylene group, 3-ethoxypentamethylene group, 1,4- (2- Methoxycyclohexane) group, phenoxyethylene group, 2-phenoxytrimethylene group, 1,3- (2-phenoxycyclohexane) group or alkylene group such as phenylethylene group,
2-phenyltrimethylene group, 1-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-bromophenylene) 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, 1,4- (2-n-dodecylphenylene) group A divalent group such as a divalent hydrocarbon group, or R ₁ is, for example, 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 Or 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,
Dihydroxybiphenyl such as 2,4'-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-fluorophenyl) -ether, bis- (4-hydroxy-3-bromophenyl)-
Ether, bis- (4-hydroxynaphthyl) -ether, bis- (4-hydroxy-3-chloronaphthyl)-
Di- (hydroxyphenyl) -such as ether, bis- (2-hydroxybiphenyl) -ether, 4,4'-dihydroxy-2,6-dimethoxydiphenyl ether, 44'-dihydroxy-2,5-diethoxydiphenyl ether
Ethers are included, 1,1-bis- (4-hydroxyphenyl) -2-phenylethane, 1,3,3-trimethyl-1- (4-hydroxyphenyl) -6-hydroxyindane, 2,4- Bis- (p-hydroxyphenyl) -4
Methylpentane is 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) _n H (where R is an alkylene oxide-derived alkylene group and one polyoxyalkylene chain contains different alkylene groups) Optionally, n is 2 or 2 which represents the polymerization number of the oxyalkylene group.
It is a compound having an atomic group of (integer above). 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 (Wherein R ₁ , R ₂ and R ₃ are the same as those in the above 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 are polyglycidyl esters of aliphatic polycarboxylic acids or aromatic polycarboxylic acids, for example, the following general formula (4)
Also included are epoxy resins obtained by polymerizing glycidyl methacrylate synthesized from epihalohydrin E and methacrylic acid.

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-
As an example of 3), an epoxy resin 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 anyline and 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
Of polyhalohydrin ether and sodium hydroxide obtained by reacting a polyhydric alcohol C having one alicyclic nucleus with epihalohydrin E in the presence of a catalytic amount of an acidic catalyst such as boron trifluoride by a conventional method. Such as an epoxy resin obtained by reacting with a basic compound such as the above or a polyhydric alcohol C having at least one alicyclic nucleus and epihalohydrin E in the conventional manner in the presence of a catalytic amount of a basic catalyst such as triethylamine. An epoxy resin obtained by reacting the polyhalohydrin ether thus obtained 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.

Further, the polyglycidyl ether compound (I-1-3) is prepared by using a polyhydric phenol having at least one aromatic nucleus in place of the above polyhydric alcohol C to form an epoxy resin, 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).

Such preferred examples of mononuclear polyhydric alcohol (C-1), general formula _{HO- (R 2) f -A- (} R 3) g -OH (2) ( wherein A is a methyl group in cyclohexane residue , An n-propyl group, an n-butyl group, an n-hexyl group, an n-octyl group, an alkyl group having preferably up to 4 carbon atoms or a halogen atom, that is, a chlorine atom, a bromine atom or a fluorine atom, or 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 flame 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 alcohol, for example, substituted or unsubstituted cyclohexanediol such as 1,4-cyclohexanediol, 2-chloro-1,4-cyclohexanediol, 1,3-cyclohexanediol, 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-dihydroxy Substitution such as propylcyclohexane, 1,4-dihydroxybutylcyclohexane or Is dihydroxyalkyl cyclohexane substituted.

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 (hydroxymethyl) -decahydronaphthalene, 1,4-
Other substituted or unsubstituted polyhydroxyalkylcycloalkanes such as bis (hydroxymethyl) -bicyclo [2.2.2] octane, dimethyloltricyclodecane are mentioned.

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 ) _g- OH (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 l are 0 or 1, but neither k nor l are 0.

R ₁ has the same definition as in the general formula (1), but from the viewpoint of flame resistance, etc., R ₁ is preferably 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 polynuclear polyhydric alcohol (C-2), particularly preferred is the general formula: HO-A _1- (R ₁ ) _j -A _2- It is a polynuclear dihydric alcohol represented by OH (3-1) (wherein A ₁ , A ₂ , R ₁ and j are the same as defined in the general formula (3)).

Preferred examples of such polynuclear dihydric alcohol include, for example, 4,
Substituted or unsubstituted bicycloalkanediol such as 4'-bicyclohexanediol, 3,3'-bicyclohexanediol, 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-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) propane, 2,2-bis (2-isopropyl-4-)
Hydroxycyclohexyl) propane, 2,2-bis (4
Bis (hydroxycycloalkyl) alkanes such as -hydroxyperhydronaphthyl) propane or 4,4 '
-Dihydroxybicyclohexane, 2,2'-dihydroxybicyclohexane, dihydroxychloroalkane such as 2,4-dihydroxybicyclohexane or bis (4
-Hydroxycyclohexyl) sulfone, 2,4'-dihydroxycyclohexyl sulfone, chloro-2,4-dihydroxydicyclohexyl sulfone, 5-chloro-4,
4'-dihydroxydicyclohexyl sulfone, 3'-
Di (hydroxycycloalkyl) sulfone such as chloro-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)
Di (hydroxy) such as ether, bis (2-hydroxybicyclohexyl) ether, 4,4'-dihydroxy-2,6-dimethoxy-dicyclohexyl ether, 4,4'-dihydroxy-2,5-diethoxydichlorohexyl ether. Cycloalkyl) ether, and 1,1-bis (4-hydroxycyclohexyl) -2-phenylethane, 1,3,3-trimethyl-1- (4-hydroxycyclohexyl) -6-hydroxyintan, 2, 4-bis (q
-Hydroxycyclohexyl) -4-methylpentane is also suitable.

Yet another such group of preferred polynuclear dihydric alcohols is of the general formula: HO-A _1- (R ₁ ) _j ‐A ₂ ‐ (R ₁ ) _j ‐A ₂ ‐OH (3-2 (In the formula, A ₁ , A ₂ , R ₁ and j are the same as defined in the general formula (3), and two R ₁ , two j and two A ₂ may be different from each other.) And 1,4-bis (4-vidroxycyclohexylmethyl) cyclohexane, 1,4
-Bis (4-hydroxycyclohexylmethyl) tetramethylcyclohexane, 1,4-bis (4-hydroxycyclohexylmethyl) tetraethylcyclohexane, 1,
4-bis (p-hydroxycyclohexylisopropyl) cyclohexane, 1,3-bis (p-hydroxycyclohexylisopropyl) cyclohexane and the like can be mentioned.

More Such polynuclear dihydric alcohol is a by another preferred group of those represented by the general _{formula: HO-R 2 -A 1 -} (R 1) j -A 2 -R 3 -OH (3-3) ( wherein A _{1, a 2, R 1,} R 2, R 3, j is those represented by the general formula (3) same as that as in defined), for example, such as 4,4'-dihydroxy methyl bicyclohexane substituted Or an unsubstituted dihydroxyalkylbicycloalkane, and 1,2-
Bis (4-hydroxymethylcyclohexyl) ethane,
Substitution such as 2,2-bis (4-hydroxymethylcyclohexyl) propane, 2,3-bis (4-hydroxymethylcyclohexyl) butane, 2,3-dimethyl-2,3-bis (4-hydroxymethylcyclohexyl) butane Alternatively, an unsubstituted bis (hydroxyalkylcycloalkyl) alkane may be mentioned.

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) _n H (where R is an alkylene group derived from alkylene oxide and one polyoxyalkylene chain contains 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 O-A ₁ (R ₁ ) _j -A 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 polyhydroxyl compound.

Still another such group of preferred polyhydroxyl compounds is of the general formula: H (OR) n ₁ O-A _1- (R ₁ ) _j -A _2- (R ₁ ) _j -A _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, n ₁ and n ₂ is a value of 1 to 3).

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 a basic 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 amine 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 Um), 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 solution.

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 dioxide, 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-
Mention may be made of epoxy-hexahydrobenzal-3,4-epoxy-cyclohexane-1,1-dimethanol and ethylene glycol-bis (3,4-epoxytetrahydro-dicyclopentadiene-8-yl) ether.

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.

Preferable examples of the urethane prepolymer (ro-1-a) used for producing the blocked isocyanate compound (ro-1) used in the present invention include, for example, polyether polyols, polyester polyols, hydroxyl group-terminated diene liquid rubbers. , Polytetramethylene ether glycol and polyisocyanate compound
An isocyanate group-containing 1 to 10 wt% having an average of more than one isocyanate group in the molecule and an average molecular weight of 600 to 20,000 obtained by reacting in the same manner as in the production method of the containing urethane prepolymer.

Preferable examples of the polyether polyols, for example the general formula R [(OR _{1) n} OH] _{p (wherein} R is a polyhydric alcohol residue; (OR _{1) n} is 2 carbon atoms
A polyoxyalkylene chain consisting of an oxyalkylene group having four alkylene groups; n is a number showing the degree of polymerization of the oxyalkylene group and corresponding to a molecular weight of 100 to 4,500; p is preferably 2 to 4 ) Is a polyether polyol.

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.), Hexahydric alcohol (eg, Solbit, Mannit, etc.)
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-mentioned polyester polyol include, for example, conventionally known polyester produced from polycarboxylic acid and polyhydric alcohol or polyester obtained from lactams. Examples of the 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, thiodipropionic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid or Any suitable carboxylic acid similar to these 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 or the like can be used.

The hydroxyl group terminated diene liquid rubber is particularly preferably hydroxyl group terminated liquid polybutadiene. The microstructure is not particularly limited. As commercial products, R-45HT made by Idemitsu Petrochemical, NISSOP BG-1000-200 made by Nippon Soda
Examples include 0.

Further, polytetramethylene ether glycol obtained by ring-opening polymerization of tetrahydrofuran can be used.

The urethane prepolymer used in the present invention is, for example, a polyether polyol or a polyester polyol as described above or a mixture thereof, a hydroxyl group-terminated liquid polybutadiene, polytetramethylene glycol or further these and OH group-containing glycerides such as castor oil. It can be obtained by reacting a mixture with 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 (Here, ○ is benzene ring or naphthalene ring,-(CH ₂ ) _m
NCO 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). -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) (for example, biphenyl-2,4'-diisocyanate, diphenyl-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 dicyclohexane-4,4'-diisocyanate, ω, ω ')
-Diisocyanate-1,2-dimethylbenzene), ω,
ω'-diisocyanate-1,3-dimethylbenzene),
Diisocyanates containing substituted urea groups obtained by reaction of 2 moles of diisocyanate with 1 mole of water (eg urea diisocyanate obtained by reaction of 1 mole of water with 2 moles of 2,4-toluylene diisocyanate), aromatic Uretdione diisocyanate, propane-1,2-diisocyanate, 2,3-dimethylbutane-2,3-diisocyanate, 2-methylpentane-2,4-diisocyanate, octane-obtained by bimolecular polymerization of diisocyanate by a known method. Examples thereof include 3,6-diisocyanate, 3,3-dinitropentane-1,5-diisocyanate, octane-1,6-diisocyanate and hexamethylene diisocyanate.

The urethane prepolymer (ro-1-a) obtained from such an isocyanate compound and the above polyhydroxyl compound such as polyether polyol, polyester polyol, hydroxyl group-terminated polybutadiene and polytetramethylene glycol can be obtained by a usual method. it can. When carrying out the urethane prepolymer formation reaction, the reaction temperature is usually 40 to 140 ° C, preferably 60 to 120 ° C. In carrying out the urethane prepolymer formation reaction, known urethane polymerization catalysts for promoting the reaction, for example, dibutyltin dilaurate, stannous octoate, organometallic compounds such as stannas octoate, triethylenediamine, triethylamine, 1,8 -Diazabicyclo (5.4.0)
It is also possible to use a tertiary amine compound such as undecene-7.

If the molecular weight of the compound (B-1-a) is less than 600, flexibility will not be obtained, and if it exceeds 20,000, compatibility with the epoxy resin will be lost.

Examples of the compound (ro-1-b) having a monovalent phenolic hydroxyl group that causes a block reaction with the NCO group-containing urethane prepolymer (ro-1-a) include phenol, cresol (metacresol, orthocresol, paracresol and Mixtures thereof), xylenol, octylphenol, nonylphenol, dinonylphenol, para-
Alkylphenols such as tert-butylphenol, sec-butylphenol, styrenated phenol, 3-methoxyphenol, 4-methoxyphenol, 4-chlorophenol, m-hydroxybenzaldehyde, o-
Examples thereof include hydroxybenzaldehyde, p-hydroxybenzaldehyde, 1-hydroxy-2-pupanone, 3-hydroxyacetophenone and hydroquinone, 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 / 2.0.

The blocking agent can be added and reacted at any stage of the above reaction to obtain the blocked isocyanate compound (b-1).

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.

Active amino group-containing compound (b-2) used in the present invention
Preferred as such are aliphatic polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, dipropylenetriamine, dimethylaminopropylamine, diethylaminopropylamine, cyclohexylaminopropylamine, monohydroxyethyldiethylenetriamine, bishydroxyethyldiethylenetriamine, N ( Aliphatic hydroxypolyamines such as 2-hydroxypropyl) ethylenediamine;
A polyamide obtained by condensation of a dimer acid and a diamine (for example, ethylenediamine); an epoxy compound (for example, ethylene oxide) having an average of less than two 1,2-epoxy groups in a stoichiometrically deficient amount of any of them. , Propylene oxide, epichlorohydrin, styrene oxide, methyl glycidyl ether, phenyl glycidyl ether, glycidyl methacrylate, etc.)
A so-called modified aliphatic amine-based curing agent obtained by the reaction with; an amine and a phenol (for example, phenol, cresol, xylenol, ethylphenol, chlorophenol, anisole) and an aldehyde or a reactive derivative of an aldehyde (for example, formaldehyde and paraformaldehyde). , And lower aliphatic aldehydes such as acetaldehyde, chloral, etc., and particularly preferably an initial condensate with formaldehyde or a reactive derivative thereof or a stoichiometrically deficient amount of 1 or more and less than 2 in the molecule Examples thereof include amine adducts (modified amines) obtained by reaction with an epoxy compound having a 1,2-epoxy group.

Further, as the compound having other amino groups contained in the active organic amino group-containing compound (b-2), piperazine,
Aliphatic amines having a cyclic structure such as N-aminoethylpiperazine and triethylenediamine; aromatic polyamines such as metaxylenediamine and paraxylylenediamine; and aromatic polyamines and phenols thereof,
Mannich salts by condensation with aldehydes; cyanoethylated polyamines.

Other trimethylhexamethylenediamine, 1,3-BAC (1,3-bisaminocyclohexylamine), Isophorone diamine Can also be used.

Particularly preferred active organic amino group-containing compounds 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 hardeners according to the invention.

More preferable other amino group-containing compound 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 its molecule, melting point 47-48 ° C, active hydrogen Although the equivalent weight is 68.6, the commercial product is a trademark of Epomate, and 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, Mitsui Texaco Co., Ltd. polyether diamine D-230, D-400, D-2000 and the following triamine T-403, The number after D- almost indicates the molecular weight. In addition, polyoxyethylene chain diamine, ED-600, ED-900, ED-2000
There is also).

Also included in the present invention are Mannich salts obtained by condensation reaction of these alicyclic amines with phenols and aldehydes, modified alicyclic polyamines, or a combination system of each of the above amines.

The reaction method of the blocked isocyanate compound (b-1) and the compound containing an active organic amino group (b-2) is as follows: reaction temperature 40 to 150 ° C, preferably 60 to 110 ° C, reaction time 1 to
It is preferable to carry out the treatment for 10 hours, preferably about 3 to 5 hours. The equivalence ratio of the reaction is preferably performed in excess of amine with respect to the blocked NCO. More preferably amino group equivalent /
Blocked NCO equivalent = 1.8-4.5.

The preferable compounding ratio of the composition of the present invention is (a) epoxy resin / (b) urea bond-containing active amine curing agent = 90 to 10/1.
It is 0 to 90 (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. Suitable diluents, extenders, reinforcing agents, fillers and pigments that may be used in the composition of the present invention include monoglycidyl ether, DOP, DBP, xylene resin, benzalcohol, tetrahydrofurfuryl alcohol, allocizer, Bituminous materials such as coal tar and bitumen, textile fibers, fibrous materials, glass fibers, synthetic fibers, asbestos fibers, boron fibers, carbon fibers, cellulose, polyethylene powder, clay, sand, rocks, quartz powder, mineral silicates such as mica and asbestos. Powder, crushed shale, kaolin,
Oxide pigments such as aluminum hydroxide, powdered chalk, gypsum, antimony trioxide, bentonite, silica aerogel, lithopone, barite, titanium dioxide, talc, calcium carbonate, carbon black, graphite, iron oxide, or Metal powder such as aluminum powder or iron powder can be used.

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 can be produced by a conventional method using a known mixing device (agitator, kneader, roller, etc.).

〔Example〕

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto.

Production Example of Blocked Isocyanate Compound 1 1000 parts of polypropylene glycol (molecular weight: 2000) and 174 parts of toluylene diisocyanate (molecular weight: 174) were placed in a four-necked flask equipped with a stirrer, a temperature system and a nitrogen inlet tube at 70 ° C. Isocyanate equivalent 1174 after reacting for 5 hours
(NCO content 3.6%) urethane prepolymer was obtained, followed by the addition of 242 parts of nonylphenol (molecular weight: 220) at 80 ℃, 5
By reacting for a time, a blocked isocyanate compound in which isocyanate groups were completely disappeared by infrared absorption spectrum was obtained (blocked isocyanate equivalent 1400).

Production Example 2 of Block Isocyanate Compound 1500 parts of polypropylene glycol (molecular weight: 3000) and 174 parts of toluylene diisocyanate are reacted in the same manner as in Reference Example 1 to obtain a urethane prepolymer having an isocyanate equivalent of 1674 (NCO content 2.5%). Further, 242 parts of nonylphenol was added and reacted in the same manner as in Production Example 1 to obtain a blocked isocyanate compound (block isocyanate equivalent: 191
6).

Curing Agent Production Example 1 Polyamide amine ACR-Hardener H-285 (amine value 4003; viscosity; 1000 cps / 25 ° C.) consisting of dimer acid / monomer acid / TTA and having an amine value of 400 blocks an isocyanate compound in 50 g.
100 g and 20 g of isophoronediamine were reacted at 100 ° C. for 3 hours to obtain a blocked isocyanate-modified polyamidoamine [A] having a viscosity (25 ° C.) of 540 ps.

Curing Agent Production Example 2 80 g of the above ACR-Hardener H-285 and 220 g of a blocked isocyanate compound were added and reacted at 100 ° C. for 4 hours to obtain a blocked isocyanate modified polyamidoamine [B] at room temperature.

Examples 1-2, Comparative Example 1 An adhesive test was conducted on the compositions shown in Table 1.

Curing Agent Production Example 3 93 g of a blocked isocyanate compound, 14 g of isophorone diamine, and 11 g of benzyl alcohol were added, and the amine / isocyanate addition reaction was carried out at 100 ° C. for 3 hours to give a viscosity (25
C.) 600 poise of product [C] was obtained.

Examples 3 to 5 and Comparative Example 2 The compositions shown in Table 2 were cured and the physical properties were measured.

Comparative Example 2 extends at −30 ° C. and loses elasticity at 0.2%.

Hardener Production Example 4 Ancamine MCA (Anchor Chemical Co. product; modified cycloaliphatec polyamine, viscosity (77 ° F) 1.8 poise,
Active hydrogen equivalent 101) 80g blocked isocyanate compound
120 g was added and an isocyanate / amino group addition reaction was carried out at 100 to 105 ° C. for 3 hours to obtain a blocked isocyanate modified amine [D]. The viscosity was (25 ° C) 150 poise.

Examples 6 to 7 and Comparative Example 3 The compositions shown in Table 3 were cured and the physical properties were examined.

Hardener Production Example 5 Isophorone diamine 2mol, phenol 1mol, formalin
To 80 g of phenol / isophoronediamine-modified Mannich compound (I) obtained by reacting 1 mol by a known method, 120 g of a blocked isocyanate compound was added, and an isocyanate / amino group addition reaction was carried out at 100 ° C. for 3 hours to obtain a blocked isocyanate / Mannich. A compound-modified amine [E], (viscosity (25 ° C.) 640 poise) was obtained.

Examples 8-9, Comparative Example 4 The adhesive properties of the compositions shown in Table 4 were measured.

Hardener Production Example 6 Polytetramethylene glycol (PTG-500) 680g, TDI-8
Using 117 g, a prepolymer formation reaction was carried out at 85 ° C. for 3 hours, and 197 g of nonylphenol and 4 g of catalyst were added to obtain 85
Blocking reaction of isocyanate nonylphenol was carried out at 4 ° C. for 4 hours to obtain a polytetramethylene glycol-based nonylphenol block compound.

Polytetramethylene glycol / TDI based nonylphenol block compound 250g, isophorone diamine 45
g and 30 g of benzyl alcohol were reacted at 100 ° C. for 3 hours to obtain a viscous blocked isocyanate-modified amine [F] at room temperature.

Examples 10 to 11 With respect to the compositions shown in Table 5, hardness and adhesiveness were measured.

Curing agent manufacturing example 7 Blocked isocyanate 200 g, isophorone diamine 10
Using 0 g and 100 g of dipharmine D-230 (polyetherdiamine, manufactured by Mitsui Texaco), reaction was carried out at 100 ° C. for 3 hours to obtain a blocked isocyanate-modified amine [G] having a viscosity (25 ° C.) of 1,800 cps.

Example 12, Comparative Example 5 The compositions shown in Table 6 were cured and the physical properties were examined.

Curing agent Production Example 8 Blocked isocyanate compound 200g Epomate B-002 200g (Oilized shell product) Dipharmine D-230 70g (Mitsui Texaco product) Block isocyanate compound / Epomate B was prepared by reacting the above mixture at 100 ° C for 3 hours. -002 / Gifarmin
A urethane-modified amine addition product [H], which was viscous at room temperature of D-230, was obtained.

Example 13, Comparative Example 6 The compositions shown in Table 7 were cured and the physical properties were examined.

[Effects of the Invention] The effects of the present invention are obtained by reacting a terminal NCO block prepolymer with phenols with an active organic amino curing agent (polyamines, modified polyamines, polyamides) in an amount such that an amino group becomes excessive, thereby producing an amine. / Urea bond generated by isocyanate reaction is introduced into the molecule of such active organic amino curing agent, and it has excellent flexibility for cured epoxy resin, especially flexibility at low temperature, and flexibility when left outdoors for a long time. And further improved amine brushability, low temperature curability and curability on the wet surface.

In addition, since the amine / isocyanate reaction is mild due to the phenolic blocking agent mask, it is easy to control the reaction, and free phenols form amine / phenolic salts, and this active organic amino cure It also has the merit of functioning as a curing accelerator for the agent.

Furthermore, one of the other effects of the present invention is that by carrying out such modification, the compatibility between the epoxy resin and the curing agent is good, and undesired phenomena such as blooming, brushing and sweating during curing are improved. Moreover, it is to provide an epoxy resin curable composition having good adhesiveness even under severe conditions such as high humidity or water.

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Claims (1)

[Claims] 1. An epoxy resin having (a) an average of more than one adjacent epoxy group in a molecule, and (b) an average of more than one in a molecule obtained from a polyhydroxy compound and an excess of a polyisocyanate compound. A urethane prepolymer having an isocyanate group content of 1 to 10% by weight and an average molecular weight of 600 to 20,000 (ro-1-a) is a compound having a phenolic hydroxyl group (ro-1-b) and NCO / phenolic hydroxyl group. Equivalence ratio = 1/1.
A urea-containing active organic compound obtained by reacting a blocked isocyanate compound (B-1) obtained by masking with 0 to 1 / 2.0 with an active organic amino group-containing compound (B-2) in excess of amine. A curable composition for an epoxy resin, which comprises an amine curing agent.