JPH03220221A - Curable composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to curable compositions. Specifically, the present invention includes:
In particular, the present invention relates to a curable epoxy resin composition that imparts flexibility, wet surface adhesion and water-swellability to an epoxy resin and is suitable as a joint material or flooring material.

[Prior art and problems to be solved by the invention] Epoxy resins have been widely used in paints, electricity, civil engineering and construction, adhesives, etc., but when cured with ordinary bisphenol A epoxy resin and polyamine, When used for civil engineering and construction purposes due to lack of flexibility, even if it has good flexibility at room temperature, it loses visibility at temperatures around O''CC and tends to become hard and brittle. This is the cause of cracks.

Various flexibility-imparting agents have been developed and put into practical use for the purpose of improving such flexibility; There were problems with temperature characteristics, physical properties, etc., and each had advantages and disadvantages.

For example, in the case of dimer acid-modified diglycidyl ether, when used for civil engineering and construction purposes, it is impractical because it is immersed in cement-resistant alkaline water, and in the case of diglycidyl ether of polyoxyalkylene glycol, it is hard to In addition, the water resistance of the cured product is also insufficient.

Furthermore, in the case of BPA-based side-chain flexible epoxy resins, water resistance and alkali resistance are improved, but flexibility remains at low temperatures, and hardening is accelerated over time, making it difficult to use when exposed for long periods of time. It is difficult to maintain flexibility if left alone.

Furthermore, flexible thiol compounds have a problem with odor. In addition, when used for structural adhesives, harsh conditions are required, especially flexibility and adhesion (tensile shear strength, T-peel) at low temperatures of -30°C. .

In order to improve such performance, urethane-modified epoxy resins and rubber-modified (CTBN) epoxies have been developed and are already in practical use, but although they improve adhesive strength and flexibility at room temperature, they are not good at low temperatures. There is a tendency for flexibility to be lost and peel strength to be significantly reduced.

We have already reported in JP-A-62-195013 that a curable composition comprising a blocked urethane/epoxy/active organic amine curing agent system has improved the above-mentioned drawbacks, and has improved the composition of conventional flexible epoxy resins and urethane-modified epoxy resins. resin,
It was also shown that the resin has extremely superior properties such as low-temperature curability, temperature-sensitive properties, especially flexibility at low temperatures, and hardness retention over time compared to rubber-modified epoxy resins.

The reason for this improvement in performance is that compared to conventional epoxy resin-based flexibility imparting agents, urethane-modified epoxy resins, and rubber-modified epoxy resins, the reaction between epoxy groups and active organic amino groups is the main reaction. In the resin obtained from the composition, in addition to the reaction between the epoxy group and the active organic amino group, the reaction between the isocyanate/amino group due to the dissociation of the blocking agent proceeds at the same time, increasing the crosslink density and incorporating urea bonds within the molecular crosslink structure. It is thought that its inclusion contributes to the improvement of physical properties.

However, the system shown in JP-A-62-195013 is
Although it has excellent flexibility as described above, satisfactory results were not obtained in terms of adhesion to wet surfaces and water-stopping properties.

[Means to solve the problem]

As a result of intensive research to solve the above problems, the present inventors have found that by using a polyol containing an oxyethylene group, it has flexibility, and also has adhesion to wet surfaces and water-swelling properties and water-stopping properties. It was discovered that a curable composition can be obtained, and the present invention was completed.

Due to its excellent performance, the curable composition of the present invention is widely used in civil engineering and construction adhesive applications.

The curable composition of the present invention contains as essential constituents: (1) an epoxy resin having an average of more than one adjacent epoxy group in the molecule; (2) a general 2R[(OR')-01]w- (wherein R is a polyhydric alcohol residue: (OR') n is an oxyethylene group or a polyoxyalkylene chain consisting of an oxyethylene group and an oxyalkylene group having an alkylene group having 3 to 4 carbon atoms, provided that the proportion of oxyethylene groups is Molecular weight 5~
It accounts for 100%. n is a number indicating the degree of polymerization of the oxyalkylene group and corresponds to a hydroxyl equivalent of 200 to 2,500; p is a number of 2 to 8, preferably 2 to 4) One or more polyether polyols represented by Isocyanate base amount obtained from a mixture of
000 urethane bond-containing compound ([2]-a) and a compound having a monohydric phenolic hydroxyl group ([2]-b) at an isocyanate group/phenolic hydroxyl group equivalent ratio=l
/1.0 to 1.5 to form a compound ([2]-a
Contains a blocked isocyanate compound obtained by masking the isocyanate group of ) with the phenolic hydroxyl group of compound ([2]-b), and (ii) an active organic amine curing agent.

The epoxy resin having an average of more than 1 adjacent epoxy group in the molecule used in the present invention includes, for example, an epoxy resin (I) having an average of more than 1.2 epoxy groups in the molecule, preferably Epoxy resin (1-1) having on average more than one substituted or unsubstituted glycidyl ether group in the molecule, Epoxy resin (1-1) having on average more than one substituted or unsubstituted glycidyl ester group in the molecule (
1-2) Epoxy resin (1-3) having an average of more than one N-substituted or unsubstituted l,2-epoxyprobyl group in the molecule (1-3) n epoxidized polyunsaturated compound (
1-4) n and other conventionally known epoxy resins containing adjacent epoxy groups.

Preferred examples of such epoxy resins (I) having an average of more than one 1,2-epoxy group in the molecule are represented by the formula: %Formula% (where Z is a hydrogen atom, a methyl group, or an ethyl group) Epoxy resin (1-1)n having on average more than one substituted or unsubstituted glycidyl ether group in the molecule Formula: % Formula % (where 2 is a hydrogen atom, a methyl group, an ethyl group) Epoxy resin (I-2)n having an average of more than one unsubstituted glycidyl ester group in the molecule Formula: Substituted or unsubstituted N-substituted represented by (where 2 is a hydrogen atom, methyl group, or ethyl group) 1. Epoxy resins (I-
3) etc.

The epoxy resin (1-1) having more than one substituted or unsubstituted glycidyl ether group in the molecule is an epoxy resin in which a phenolic hydroxyl group is glycidyl etherified, and an epoxy resin in which an alcoholic hydroxyl group is glycidyl etherified. Preferred examples of such epoxy resins (1-1) include polyglycidyl ethers of polyhydric phenol A (1-1-1) having one or two or more aromatic nuclei; Polyglycidyl ether (1-1-2) of alcoholic polyhydroxyl compound B derived from the addition reaction of polyhydric phenol A having 1 or more aromatic nuclei and alkylene oxide having 2 to 4 carbon atoms and 1 or polyglycidyl ether of polyhydric alcohol C having two or more alicyclic nuclei (
I-1-3) and an alcoholic polyhydroxyl compound derived by an addition reaction between a polyhydric alcohol C having one or more alicyclic nuclei and an alkylene oxide having 2 to 4 carbon atoms. Glycidyl ether (1-
1-4), etc.

However, polyglycidyl ether (1-1-1) is
For example, polyhydric phenol A having a small amount (all of which has one aromatic nucleus) and epihalohydrin E are reacted in a conventional manner in the presence of a basic catalyst such as sodium hydroxide or a reactive amount of a basic compound. at least one epoxy resin containing glycidyl ether as a main reaction product;
Polyhalohydrin ether obtained by reacting polyhydric phenol A having aromatic nuclei with epihalohydrin E in the presence of an amount of an acidic catalyst such as boron trifluoride, and a basic compound such as sodium hydroxide. Epoxy resins such as those obtained by reacting with compounds or polyhydric phenols A having at least one aromatic nucleus and ebihalohydrin E in the presence of a catalytic amount of a basic catalyst such as triethylamine in a conventional manner. It is an epoxy resin obtained by reacting a halohydrin ether with a basic compound such as sodium hydroxide.

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

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

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

Further, as an example of the polynuclear polyhydric phenol (A-2), the general formula: [In the formula, Ar is an aromatic divalent hydrocarbon such as a naphthylene group or a phenylene group, and a phenylene group is preferable for the purpose of the present invention. + and Y may be the same - or different,
Alkyl groups such as methyl, n-propyl, n-butyl, n-hexyl, n-octyl, preferably with up to 4 carbon atoms, or halogen atoms, i.e. chlorine, bromine, iodine Atom or fluorine atom or an alkoxy group such as methoxy, methoxymethyl, ethoxy, ethoxyethyl, n-butoxy, amyloxy is an alkoxy group having up to 4 carbon atoms.

When a substituent other than a hydroxyl group is present in either or both of the above aromatic divalent hydrocarbon groups, these substituents may be the same or different. O(
An integer with a value from zero) to a maximum value, which can be the same or different. R8 is, for example, -C-, -O-,
-S-.

1 -5o-, -5Ot-1 or alkylene groups such as methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, 2-ethylhexamethylene group, octamethylene group, nonamethylene group,
Decamethylene group, or alkylidene group such as ethylidene group, propylidene group, isopropylidene group, isobutylidene group, amylidene group, isobutylidene group, 1-phenylethylidene group, or cycloaliphatic group such as 1,4-
Cyclohexylene group, 1,3-cyclohexylene group, cyclohexylidene group, or halogenated alkylene group or halogenated alkylidene group, or halogenated cycloaliphatic group, or alkoxy- and alkoxy- Substituted alkylidene groups or alkoxy- and aryloxy-substituted alkylene groups or alkoxy- and aryloxy-substituted cycloaliphatic groups such as methoxymethylene, ethoxymethylene, ethoxyethylene, 2-ethoxytrimethylene groups , 3-ethoxypentamethylene group, 1.4-(2-methoxycyclohexane) group, phenoxyethylene group, 2-
phenoxytrimethylene group, 1,3-(2-phenoxycyclohexane) group, or ary-substituted alkylene group such as phenylethylene group, 2-phenyltrimethylene group, 1-phenylpentamethylene group, 2-phenyldeca Methylene group, or aromatic group 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 alkoxy- and aryloxy-substituted aromatic groups such as 1.4-(2-methoxyphenylene) group, 1.4-(2,- ethoxyphenylene) group,
1.4(2-n-propoxyphenylene) group, 1,4(
2-phenoxyphenylene) group, or an alkyl-substituted aromatic group such as 1.4-(2-methylphenylene) group, 1.4-(2-ethylphenylene) group, 1.4
-(2-n-propylphenylene) group, 1.4-(2-
n-butylphenylene) group, 1,4-(2-n-dodecylphenylene) group, or L is a divalent group such as a divalent hydrocarbon group such as Alternatively, R1 may be a polyalkoxy group such as a polyethoxy group, a polypropoxy group, a polythioethoxy group, a polybutoxy group, a polyphenylethoxy group, etc. or L can be a group containing a silicon atom, such as a polydimethylsiloxy group, a polydiphenylsiloxy group, a polymethylphenylsiloxy group, or L can be an aromatic ring, a tertiary-amino group, an ether There are polynuclear dihydric phenols which can be two or more alkylene or alkylidene groups separated by a bond, a carbonyl group or a sulfur-containing bond such as sulfur or sulfoxide.

Among these polynuclear dihydric phenols, particularly preferred are those having the general formula (wherein Y' and Y have the same meanings as above, and
has a value of 0 to 4, and R is preferably an alkylene or alkylidene group having 1 to 3 carbon atoms or a saturated group of the formula.

Examples of such dihydric phenols include 2,2-bis-(p-hydroxyphenyl)-propane, commonly referred to by the trade name bisphenol A, 2,4'-dihydroxydiphenylmethane, and bis-(2-hydroxyphenyl)-methane. ,
Bis-(4-hydroxyphenyl)-methane, bis-(
4-Hydroxy-2,6-dimethyl-3-methoxyphenyl)-methane, 1.1-bis-(4-hydroxyphenyl)-ethane, 1.2-bis-(4-hydroxyphenyl)-ethane, 1.1 -bis-(4-hydroxy-2
-chlorophenyl)-ethane, 1,1-bis-(3,5
-dimethyl-4-hydroxyphenyl)-ethane, 1.
3-bis-(3-methyl-4-hydroxyphenyl)-
Propane, 2,2-bis-(3,5-dichloro-4=hydroxyphenyl)-propane, 2,2-bis-(3-
Phenyl-4-hydroxyphenyl)-propane, 2,
2-bis-(3-isopropyl-4-hydroxyphenyl)-propane, 2.2-bis-(2-isopropyl-
4-hydroxyphenyl)-propane, 2,2-bis-
(4-hydroxynaphthyl)-propane, 2,2-bis-(4-1 nitroxyphenyl)-pentane, 3,3-bis-(4-hydroxyphenyl)-pentane, 2,2-
Bis-(4-hydroxyphenyl)-hebutane, bis-
(4-hydroxyphenyl)-methane, bis-(4-hydroxyphenyl)-cyclohexylmethane, 1.2-
Bis-(4-hydroxyphenyl)-1,2-bis-(
bis-(hydroxyphenyl)alkanes such as phenyl)-propane, 2,2-bis-(4-hydroxyphenyl)-1-phenylpropane or 4°4'-dihydro, xybiphenyl, 2,2'-dihydroxybiphenyl , dihydroxybiphenyl such as 2,4'-dihydroxybiphenyl or bis-(4-hydroxyphenyl)
-sulfone, 2,4'-dihydroxydiphenylsulfone, chlor2,4-dihydroxydiphenylsulfone,
Di(hydroxyphenyl)-sulfone or bis(4-hydroxyphenyl)-ether, such as 5-chloro-4,4°-dihydroxydiphenylsulfone, 3'-chloro-4,4"-dihydroxydiphenylsulfone, 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-bromphenyl)-ether, bis-(4-hydroxynaphthyl)-ether, bis-(4- hydroxy-3-chlornaphthyl)-ether, bis-(2-hydroxybiphenyl)-ether, 4,4'-dihydroxy-2,
Includes di(hydroxyphenyl)-ethers such as 6-simethoxydiphenyl ether, 4,4''-dihydroxy-2,5-jethoxydiphenyl ether, and also 1,1-bis-(4-hydroxyphenyl)- 2-phenylethane, 1.3.3-trimethyl-1-(4-hydroxyphenyl)-6-hydroxyindan, 2,4
-bis-(p-hydroxyphenyl)-4-methylpentane is also suitable.

Furthermore, another preferred group of such polynuclear dihydric phenols has the general formula (where R4 is a methyl or ethyl group, Rt and Rx are each an alkylidene group having 1 to 9 carbon atoms or other alkylene group, q is O~4), such as 1.4-bis-(4-hydroxybenzyl)-benzene, 1.4-bis-(4-hydroxybenzyl)-tetramethylbenzene, 1.4-bis= (4-hydroxybenzyl)-tetraethylbenzene, 1.4-bis-(p-hydroxycumyl)-benzene, 1.3-bis-(p-hydroxycumyl)-benzene, and the like.

Other polynuclear polyhydric phenols (A-2) include, for example, initial condensates of phenols and carbonyl compounds I! (Example: phenolic resin initial condensate, condensation reaction product of phenol and acrolein, phenol and glyoxal condensation reaction product, condensation reaction product of phenol and pentanediallyl, condensation reaction product of resorcinol and acetone, xylene-phenol- Formalin initial condensation products)NCondensation reaction products of phenols and polychloromethylated aromatic compounds (eg, condensation reaction products of phenol and bischloromethylxylene), etc. can be mentioned.

Therefore, the polyhydroxyl compound B here refers to the above-mentioned polyhydric phenol A having at least one aromatic nucleus and alkylene oxide in the presence of a catalyst that promotes the reaction between the 011 group and the epoxy group. -R'OR (here R'' is an alkylene group derived from alkylene oxide) or (and) -(R''0)n% which is bonded to the phenol residue by an ether bond obtained by reaction
・H (Here, R'' is an alkylene group derived from alkylene oxide, and one polyoxyalkylene chain may contain different alkylene groups, n is an integer of 2 or more indicating the number of polymerized oxyalkylene groups) It is a compound that has the following atomic group.

In this case, the ratio of the polyhydric phenol A to the alkylene oxide is 1:1 (mol: mol) or more, but preferably the ratio of the alkylene oxide to the OH group of the polyhydric phenol A is 1:1 to 10. , preferably l:
1 to 3 (equivalent: equivalent).

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

A particularly preferable group of such polyhydroxyl compounds has the general formula (where 'ZYI+Il+2 and i is the same as that of the above formula (1-1), and R'' is an alkylene group having 2 to 4 carbon atoms. , nl and n2 are values of 1 to 3).

Furthermore, another preferred group of such polyhydroxyl compounds has the general formula (R1+R3J4+Q
is the same as that in formula (1-2) above, and "is carbon number 2
-4 alkylene groups, nl and n2 have values of 1 to 3).

Therefore, the polyglycidyl ether (1-1-3) of polyhydric alcohol C having one or more alicyclic nuclei is, for example, polyglycidyl ether (1-1-3) of polyhydric alcohol C having at least one alicyclic nucleus and shrimp halohydrin. Epoxy resin containing as a main reaction product a polyglycidyl ether obtained by reacting E with a basic catalyst such as sodium hydroxide or a reactive amount of a basic compound in the presence of a reaction amount of a basic catalyst or a basic compound, an epoxy resin containing at least one alicyclic ring as a main reaction product. A polyhalohydrin ether obtained by reacting a polyhydric alcohol C having a group nucleus and an epihalohydrin E in the presence of a catalytic amount of an acidic catalyst such as boron trifluoride in a conventional manner and a basic compound such as sodium hydroxide. or by reacting a polyhydric alcohol C having at least one alicyclic nucleus with epihalohydrin E in a conventional manner in the presence of a catalytic amount of a basic catalyst such as triethylamine. It is an epoxy resin obtained by reacting polyhalohydrin ether with a basic compound such as sodium hydroxide.

Similar polyglycidyl ether compound (■-14) is
For example, a polyhydroxyl compound derived by an addition reaction between a polyhydric alcohol C having at least one alicyclic nucleus and an alkylene oxide having 2 to 4 carbon atoms and shrimp halohydrin E are combined with an acidic catalyst such as boron trifluoride. An epoxy resin containing as a main reaction product a polyglycidyl ether obtained by reacting a polyhalohydrin ether obtained by a conventional method with a basic compound such as sodium hydroxide in the presence of a catalytic amount of Among these, preferred are polyglycidyl ethers of polyhydric alcohols having one or more alicyclic nuclei and one
Examples thereof include polyglycidyl ethers of alcoholic polyhydroxyl compounds derived by an addition reaction between a polyhydric alcohol having one or more alicyclic nuclei and an alkylene oxide having 2 to 4 carbon atoms.

In addition, the polyglycidyl ether compound (I-1-3) is small (polyhydric phenol having one aromatic nucleus is used instead of the polyhydric alcohol C to make an epoxy resin, and then the aromatic nucleus is hydrogenated. It can also be obtained as an alicyclic nucleus by doing this.

Examples of catalysts that can be used in this case include catalysts in which rhodium or ruthenium is supported on a carrier, as described in Japanese Patent Publication No. 7788/1988.

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

Preferred examples of such mononuclear polyhydric alcohols (C-1) include the general formula % formula % (2) (in the formula, ^ is a cyclohexane residue, methyl group, n-propyl group, n-butyl group, n-hexyl group). alkyl groups, preferably with up to 4 carbon atoms, such as n-octyl groups, or halogen atoms, i.e. chlorine atoms,
Substituted with bromine or fluorine atoms, or alkoxy groups such as methoxy, methoxymethyl, ethoxy, ethoxyethyl, n-butoxy, amyloxy, preferably with alkoxy groups having up to 4 carbon atoms. It may or may not be substituted, but from the viewpoint of flame resistance, halogen substitution or no substitution is preferable.

P and R4 may be the same or different, for example, an alkylene group such as methylene group, n-propylene group, n-butylene group, n-hexylene group, n-octylene group (is an alkylene group having up to 6 carbon atoms). It is an alkylene group with atoms,
f and g are O or l, preferably O), such as 1,4-cyclohexanediol, 2-chloro-1,4-cyclohexanediol, Substituted or unsubstituted cyclohexanediols such as 1,3-cyclohexanediol, 2-methyl 1,4-cyclohexanediol and 1,4-dihydroxymethylcyclohexane, 2-
chloro-1,4-dihydroxymethylcyclohexane,
1.3-dihydroxymethylcyclohexane, 1゜4-
There are substituted or unsubstituted dihydroxyalkylcyclohexanes such as dihydroxyethylcyclohexane, 1,3-dihydroxyethylcyclohexane, 1,4-dihydroxypropylcyclohexane, and 1,4-dihydroxybutylcyclohexane.

Furthermore, other mononuclear polyhydric alcohols having one alicyclic residue include 1,3-cyclobentanediol, 1,3
-Cycloheptanediol, 1゜4-cycloheptanediol, 1.3-cycloheptanediol, 1,5-perhydronaphthalenediol, 1.3-dihydroxy-
2,2,4,4-tetramethylcyclobutane, 2,6-
Other substituted or unsubstituted cycloalkyl polyols such as cyhydroxy-decahydronaphthalene, 2,7-dihydroxy-decahydronaphthalene, 1,5-dihydroxy-decahydronaphthalene and 1,3-dihydroxymethylcyclopentane, 1, 4-dihydroxymethylcycloheptane, 2.6-bis(hydroxymethyl)-decahydronaphthalene, 2.7-bis(hydroxymethyl)
-decahydronaphthalene, l,5-bis(hydroxymethyl)decahydronaphthalene, 1,4-bis(hydroxymethyl)-decahydronaphthalene, 1,4-bis(hydroxymethyl)-bicyclo(2,2,2) octane,
Other substituted or unsubstituted polyhydroxyalkylcycloalkanes include dimethyloltricyclodecane.

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

In addition, as an example of a polynuclear polyhydric alcohol (C-2), the general formula: % formula % (3) (where h and A2 are monocyclic or polycyclic divalent alicyclic hydrocarbon residues and a methyl group , n-propyl group, n-butyl group,
Alkyl groups, preferably with up to 4 carbon atoms, such as n-hexyl, n-octyl, or halogen atoms, i.e. base atoms, bromine or fluorine atoms, or methoxy, methoxymethyl, ethoxy groups , ethoxyethyl group, n-butoxy group, alkoxy group such as amyloxy group, which may or may not be substituted with an alkoxy group preferably having up to 4 carbon atoms, but from the viewpoint of flame resistance. is preferably halogen-substituted or unsubstituted.

K and are O or 1, but k and are never both 0.

R2 is the same as defined in the general formula (1) above,
From the viewpoint of flame resistance, etc., methylene groups, ethylene groups, and isopropylene groups are preferable.

j is 0 or l.

R2 and R6 may be the same or different, e.g. alkylene groups such as methylene, n-propylene, n-butylene, n-hexylene, n-octylene, preferably having up to 6 carbon atoms. is an alkylene group,
f and g are 0 or 1, preferably 0. i
is a number of 0 or more, preferably O or 1).

Among such polynuclear dihydric alcohols, particularly preferred are polynuclear dihydric alcohols represented by the general formula: It's alcohol.

Preferred examples of such polynuclear dihydric alcohols include 4.
Substituted or unsubstituted bicycloalkanediols 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, l, l-
Bis-(4-hydroxycyclohexyl)propane, 1
．． 1-bis-(4-hydroxycyclohexyl)butane, 1゜l-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)hebutane, 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, l,2-bis(4-hydroxycyclohexyl)ethane, 1.1-bis(4-hydroxy-2-chlorocyclohexyl)ethane, l,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-
Bis(hydroxycycloalkyl)alkanes such as 4-hydroxycyclohexyl)propane, 2.2-bis(4-hydroxyperhydronaphthyl)propane or 4.4"-dihydroxybicyclohexane, 2.2'-
Dihydroxycycloalkanes such as dihydroxybicyclohexane, 2,4-dihydroxybicyclohexane or bis(4-hydroxycyclohexyl)sulfone, 2,4°-dihydroxycyclohexylsulfone, chlor-2,4-dihydroxydicyclohexyl Sulfone, di(hydroxycycloalkyl)sulfone such as 5-chloro-4,4'-dihydroxydicyclohexylsulfone, 3"-chloro-4,4'-dihydroxydicyclohexylsulfone or bis(4-hydroxy cyclohexyl) 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)ni,thyl,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-hydroxybicyclohexyl) ether, 4゜4
Di(hydroxycycloalkyl) ethers such as °-dihydroxy-2,6-simethoxydicyclohexyl ether, 4,4°-dihydroxy-2°5-jethoxydicyclohexyl ether, and 1,1-bis( 4-hydroxycyclohexyl)-2-phenylethane, 1.3.3-trimethyl-1-(4-hydroxycyclohexyl)-6-hydroxyindan, 2.4-
Bis(P-hydroxycyclohexyl)-4-methylpentane is also suitable.

Furthermore, another preferable group of such polynuclear dihydric alcohols has the general formula: 112 j12 6 may be different), for example, 1.4-
Bis(4-hydroxycyclohexylmethyl)cyclohexane, l,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.

Furthermore, another preferable group of such polynuclear dihydric alcohols has the general formula: % formula % (33) (where ^t+At+R+Js+Rh+3 is the general formula (
3)), for example, substituted or unsubstituted dihydroxyalkylbicycloalkanes such as 4,4'-dihydroxydimethylbicyclohexane, and 1,2-bis(4-hydroxy methylcyclohexyl)ethane, 2,2-bis(4-hydroxymethylcyclohexyl)propane, 2,3-bis(4-hydroxymethylcyclohexyl)butane, 2,3-dimethyl-2°3-bis(4-hydroxymethylcyclohexyl) ) Substituted or unsubstituted bis(hydroxyalkylcycloalkyl)alkanes such as butane.

Here, the polyhydroxy compound refers to the above-mentioned polyhydric alcohol C having at least one alicyclic nucleus and an alkyl oxide in the presence of a catalyst that promotes the reaction between the OH group and the epoxy group. It is bonded to the alicyclic residue through an ether bond obtained by reacting with. -R”
OH (here R” is an alkylene group derived from alkylene oxide) or (and)-(R”o)nt-tt
(Here, R'' is an alkylene group derived from alkylene oxide, and one polyoxyalkylene chain may contain different alkylene groups. n' is an integer of 2 or more indicating the number of polymerized oxyalkylene groups) It is a compound having an atomic group. In this case, the ratio of the polyhydric alcohol C and alkylene oxide is 1:1 (mol: mol) or more, but preferably the OH of the polyhydric alcohol C
The ratio of alkylene oxide to groups is 1:1O~I
O1 is particularly preferably 1 to 3 (equivalent: equivalent).

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

A particularly preferred group of such polyhydroxyl compounds has the general formula: %Formula%) (wherein AI+Al+RI+J is the same as that in the general formula (3-1), and R'' has 2 to 4 carbon atoms. is a polyhydroxyl compound represented by an alkylene group, n, and n2 are values of 1 to 3).

Another preferable group of such polyhydroxyl compounds is the general formula: % formula % (wherein ^, Ao, and R0j are the same as those in the general formula (3-2), and R ” is an alkylene group having 2 to 4 carbon atoms,
n8 and n2 are values of 1 to 3).

Among these -nuclear or polynuclear polyhydric alcohols C, particularly preferred are those containing one cyclohexane ring as an alicyclic residue.
or two, among which dihydroxymethylcyclohexane and 2°2-bis(4-hydroxycyclohexyl)propane are preferred.

In addition, the epoxy resin (1-2) having an average of more than one substituted or unsubstituted glycidyl ester group in the molecule,
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 shown in ) and methacrylic acid.

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

In addition, epihalohydrin E herein is represented by the general formula: (where Z is a hydrogen atom, a methyl group, an ethyl group, and Xo is a halogen atom), and examples of such epihalohydrin E include, for example, epichlorohydrin. , shrimp bromohydrin, 1,2-epoxy-2methyl-3-chloropropane, 1,2-epoxy-2-ethyl-3-chloropropane, and the like.

The acidic catalyst that promotes the reaction between epihalohydrin E and polyhydric phenol A, polyhydroxyl compound B, polyhydric alcohol C, or polyhydroxyl compound R is as follows:
Lewis acids such as boron trifluoride, stannic chloride, zinc chloride, and ferric chloride, derivatives exhibiting these activities (e.g., boron trifluoride-ether complex compounds), or mixtures thereof can be used. .

Similarly, as a basic catalyst for promoting the reaction between epihalohydrin E and polyhydric phenol A1 polyhydroxyl compound B1 polyhydric alcohol C or polyhydroxyl compound R, alkali metal hydroxide (e.g. sodium hydroxide) is used.
n Alkali metal alcoholades (e.g. sodium ethylate) n Tertiary amine compounds (e.g. triethylamine,
triethanolamine) n quaternary ammonium compound (
(e.g., tetramethylammonium bromide) or mixtures thereof can be used, and either the glycidyl ether is formed simultaneously with such a reaction, or the halohydrin ether formed as a result of the reaction is ring-closed by a dehydrohalogenation reaction. As the basic compound for producing glycidyl ether, alkali metal hydroxides (eg, sodium hydroxide), alkali metal salts of aluminate (eg, sodium aluminate), and the like are conveniently used.

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

Acidic catalysts have a large catalytic effect to promote the reaction between epihalohydrin E and polyhydric phenol A, polyhydroxyl compound B, polyhydric alcohol C, or polyhydroxyl compound.

Furthermore, polyglycidyl ether compounds obtained by reacting mixtures of the above polyhydric alcohols with epihalohydrin can also be used in the compositions of the present invention.

Further, examples of the epoxidized polyunsaturated compound (I4) include epoxidized polybutadiene (so-called oxylon) n-vinylcyclohexene dioxide, limonene dioxide, dicyclopentanediene dioxide,
Bis(3゜4-epoxycyclohexylmethyl) phthalate, diethylene glycol-bis(3,4-epoxy-cyclohexenecarboxylate) n3゜4-epoxy-6-methyl-cyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate Hoxiley) n3
．． Mention may be made of 4-epoxy-hexahydrobenzal-3,4-epoxy-cyclohexane-1,1-dimetatool and ethylene glycol-bis(3,4-epoxytetrahydro-dicyclopentadien-8-yl) ether. can.

In addition, conventionally known epoxy resins containing adjacent epoxy groups, such as various epoxy resins described in "Production and Application of Epoxy Resins" (edited by Hiroshi Kakiuchi), may be used.

The urethane bond-containing compound ([2]-a) used in the present invention for producing the blocked isocyanate compound (2) used as a flexibility imparting agent for epoxy resins is a polyether represented by the following general formula (5). 1 to 10% by weight of isocyanate groups obtained by reacting one type or a mixture of two or more polyols and a polyisocyanate compound in the same manner as in the production method of a normal NCO-containing urethane prepolymer;
It has an average molecular weight of 600 to 10,000.

The above polyether polyol has the general formula % formula % (5) (where R is a polyhydric alcohol residue: (0 [?') n is an oxyethylene group or an oxyethylene group and a carbon number of 3 to
A polyoxyalkylene chain consisting of an oxyalkylene group having 4 alkylene groups, provided that the proportion of oxyethylene groups is 5 to 100% of the molecular weight (especially 20 to 80% by weight when imparting appropriate water swellability) . n is a number indicating the degree of polymerization of the oxyalkylene group, and the hydroxyl group equivalent is 200 to
A number corresponding to 2500: p is a polyether polyol represented by a number from 2 to 8, preferably from 2 to 4.

Preferred examples of polyhydric alcohols corresponding to OR in the above general formula include aliphatic dihydric alcohols (e.g. ethylene glycol, propylene glycol, 1,4-butylene glycol, neopentane glycol) n trihydric alcohols (e.g. 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, 1.2.4pentanetriol, trimethylolpropane, etc.) n 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 alcohols (eg, adonite, arapinto, xylit, etc.), hexahydric alcohols (eg, sorbitol, mannitol, idit, etc.), and the like.

Also, preferred as the polyhydric alcohol are dihydric to tetrahydric alcohols, with propylene glycol, glycerin and the like being particularly preferred.

In addition, the polyether polyol represented by the above general formula (5) is prepared by adding ethylene oxide or ethylene oxide and an alkylene oxide having 3 to 4 carbon atoms to the polyhydric alcohol by a conventional method so that the proportion of oxyethylene groups is equal to the molecular weight. It accounts for 5 to 100%, and the hydroxyl equivalent is 200 to 25.
It can be manufactured by adding it so that it becomes 00.

Urethane bond-containing compound ([2]-
a) is, for example, one of the polyether polyols as described above.
It can be obtained by reacting a species or a mixture of two or more species with a polyisocyanate.

In addition, as the polyisocyanate compound here, the general formula (where O is a benzene ring or a naphthalene ring, -NCQ
is a nuclear-substituted isocyanate group, Z is a nuclear-substituted halogen atom or an alkyl or alkoxyl group having 3 or less carbon atoms, and l is 0.1 or 2) (for example, 2.4-tolylene diisocyanate, 2.6 −)
Louis diisocyanate, 1,4-naphthylene diisocyanate, 1,5-naphthylene diisocyanate, 1
．． 3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 1-isopropylbenzo-2
．． 4-diisocyanate) general formula (where ○ is a benzene ring or naphthalene ring, -(CH
2) n NGO is a nuclear-substituted alkylene isocyanate group, 2 is a nuclear-substituted halogen atom or an alkyl or alkoxyl group having 3 or less carbon atoms, ■ is l or 2, l is 1 or 2) diisocyanate (e.g. ω) , ω°-diisocyanate 1,2-dimethylpenzole, ω, ωゝ-diisocyanate 1,3-dimethylpenzole) (% formula %) (where B is -C1,- or C113-C- Alkylene group having 3 or more carbon atoms such as C1h, ○ is a benzene ring or naphthalene ring, 2 is a nuclear-substituted halogen atom or an alkyl or alkoxy group having 3 or less carbon atoms, j and ll are 0,
1 or 2) (e.g. 4, 4)
'-Diphenylmethane diisocyanate, 2,2'-dimethyldiphenylmethane-4,4°-diisocyanate, diphenyldimethylmethane-4,4°-diisocyanate, 3,3'-dichlorodiphenyldimethylmethane-4
, 4'-diisocyanate)n General formula () (where Z is a nuclear-substituted halogen atom or an alkyl or alkoxy group having 3 or less carbon atoms, 1 is 0 or 1, and 0 is 0)
．． 1 or 2) (e.g. biphenyl-2,4''-diisocyanate, biphenyl-4,
4′-diisocyanate, 3.3′-dimethylbiphenyl-4,4°-diisocyanate) n3.3′-dimethoxybiphenyl-4,4°-diisocyanate) n diphenylsulfone-4,4′-diisocyanate, included in the above isocyanate Diisocyanates such as those obtained by hydrogenating the aromatic ring of
-dimethylcyclohexane, ω,ω diisocyanate 1.3-dimethylcyclohexane) n Diisocyanate containing substituted urea groups obtained by reaction of 2 mol of diisocyanate and 1 mol of water (e.g. 1 mol of water and 2 mol of 2.4 - urea diisocyanate obtained by reaction with toluylene diisocyanate) n uretdione diisocyanate obtained by bimolecular polymerization 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-
Examples include 1,6-diisocyanate and hexamethylene diisocyanate.

A urethane bond-containing compound obtained from such an isocyanate compound and the above-mentioned polyether polyol (
[2]-a) can be obtained by a conventional method. When performing a reaction for producing a urethane bond-containing compound, the reaction temperature is usually 40 to 140°C, preferably 60 to 120°C. When carrying out the reaction for producing a urethane bond-containing compound, known catalysts for urethane polymerization such as organometallic compounds such as dibutyltin dilaurate, stannous octoate, stannous octoate, triethylenediamine, triethylamine, 1, It is also possible to use tertiary amine compounds such as 8-diazabicyclo(5,4,0)undecene-7.

If the molecular weight of the above compound ([2]-a) is less than 600, it will not exhibit flexibility, and if it exceeds 10,000, it will lose compatibility with the epoxy resin.

A compound having a monovalent phenolic hydroxyl group ([
2]-b) include phenol, cresol (metacresol, orthocresol, para-cresol and mixtures thereof), xylenol, octylphenol, nonylphenol, dinonylphenol, para-tert;
Examples include alkylphenols such as -butylphenol and 5ec-butylphenol, styrenated phenols, and mixtures of two or more of these phenols.

The isocyanate/phenol blocking reaction is carried out by a known reaction method. Reaction temperature is 50℃~150℃
C1 is preferred, and more preferably 70 DEG C. to 120' C1 reaction time is preferably about 1 to 7 hours. The equivalent ratio is isocyanate group/phenolic hydroxyl group = 1/1.0 ~
It is 1.5.

The blocking agent can be added at any stage of the above reaction and reacted to obtain blocked isocyanate compound (2).

Possible methods of addition include adding at the end of a predetermined polymerization, adding at the beginning of the polymerization, or adding a portion at the beginning of the polymerization and adding the remainder at the end of the polymerization.

It is also possible to accelerate the reaction by adding a known catalyst for urethane polymerization during the zero reaction, which is preferably a method of adding at the end of polymerization.

Preferred active organic amine curing agents (2) used in the present invention include fatty acids such as ethylenediamine, diethylenetriamine, triethylenetetramine, dipropylenetriamine, dimethylaminopropylamine, diethylaminopropylamine, cyclohexylaminopropylamine, etc. family polyamines, monoethanolamines,
Aliphatic hydroxymonoamines such as jetanolamine, propatoolamine, N-methylethanolamine, etc.; aliphatic such as aminoethylethanolamine, monohydroxyethyldiethylenetriamine, bishydroxyethyldiethylenetriamine, N-(2-hydroxypropyl)ethylenediamine, etc. Hydroxy polyamines; polyamides obtained by condensation of dimer acids and diamines (e.g. ethylenediamine); epoxy compounds having an average of less than two 1,2-epoxy groups in the molecule in stoichiometrically insufficient amounts with either of these ( (e.g. ethylene oxide, propylene oxide, epichlorohydrin, styrene oxide, methyl glycidyl ether, phenyl glycidyl ether, glycidyl methacrylate, etc.)
So-called modified aliphatic amine curing agents obtained by reaction with; aniline, toluidine, ethylaniline, xylidine, benzidine, 4,4'-diaminodiphenylmethane, 2.4.6-)(dimethylaminomethyl)phenol, 2 .2-bis(4-aminophenyl)propane,
4,4'-diaminodiphenyl ether, 4'4'-diaminodiphenyl sulfone, 4,4'-diaminobenzophenone, 2,2''-dimethyl-4,4'-diaminodiphenylmethane, 2,4'-diaminobiphenyl, 3.
3′-dimethyl-4,4”-diaminobiphenyl, 3,
Aromatic amines such as 3'-dimethoxy-4,4'-diaminobiphenyl, such aromatic amines and aldehydes, or reactive derivatives of aldehydes (e.g. formaldehyde, paraformaldehyde, acetaldehyde, aliphatic lower aldehydes such as chloral) are mentioned,
.

Initial condensates of such aromatic amines with phenol 11 (e.g. phenol, cresol, xylenol,
An initial condensation product of ethylphenol, chlorophenol, phenol) and the above-mentioned aldehyde or a reactive derivative of aldehyde, or an average of 1 or more and less than 2 1.2- These include amine adducts (modified amines) obtained by reaction with epoxy compounds having epoxy groups.

In addition, other curing agents having amino groups included in the active organic amine curing agent (1) include aliphatic amines having a cyclic structure such as piperazine, N-aminoethylpiperazine, and triethylenediamine; metaphenylene diamine, metaxylene dimine, Aromatic-class amines such as paraxylene diamine, p, p”-diaminodiphenylmethane, diaminophenyl sulfone: benzyldimethylamine, 2-
Methyldimethylamine, tri(dimethylaminomethyl)
Aromatic tertiary amines such as benzene, BF3 ・CtHs
Examples include NHz, BFs/piperazine, trialkanolamine borate; titanic acid amino acid; cyanoethylated polyamine; melamine resin initial condensate, and amino resin initial condensate.

Others trimethylhexamethylene diamine, NHz-C
)lx-C-C)lx-CI-Cut-CL-NHzH
s Isophorone diamine can also be used.

Particularly preferred active organic amine curing agents are those with one or more cycloaliphatic rings, examples of which include 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, 3,3°-dimethyl-4,4°-diaminodicyclohexylmethane and 3-aminomethyl-3,3,
5-) Limethyl-cyclohexylamine. Di-primary cycloaliphatic amines are particularly suitable for the compositions of the invention.

More preferred other amine curing agents include 3.9-
Bis(3-aminopropyl)-2,4,8,10-tetraspiro(5,5)undecane (ATU) (ATU is a diamine with a unique structure as shown below that contains a spiro ring in the molecule, and has a melting point of 47 ~48°C, active hydrogen equivalent 68.
6, but the commercially available product is a trademark of Epomate, and has been modified in various ways to become a liquid curing agent.

Derivatives of the above compounds, epoxy adducts, acrylonitrile adducts, diamines with a hydantoin ring, 0 Rz (R+, Rt is hydrogen or lower alkyl group), and triamines with an ether bond in the main chain (these series of diamines include There are polyoxypropylene chain amines with the following structure. Specifically, Mitsui Texaco's polyether diamine D
-230, 0-400, D-2000 and T-4 below
There is a triamine number 03, and the number after rho roughly represents the molecular weight.

Also, polyoxyethylene chain diamine, [! D-600
There are also ゜HD-900 and HD-2000).

In addition, other nitrogen atom-containing curing agents such as dicyandiamide, guanidine, polycarboxylic acid hydrachitate,
Alternatively, imidazole and imidazole derivatives may be mentioned as latent curing agents.

In the present invention, it is desirable to create a composition in which the molecular weight of the blocked isocyanate compound, the EO content, and the blending ratio with the epoxy resin are varied depending on the use and purpose of use.

Generally speaking, when the purpose is to stop water by utilizing water swelling property, block isocyanate is used. The molecular weight is thick ((
The hydroxyl equivalent of the polyether polyol is 1000 to 25
00 is preferred) n The ratio of epoxy resin is small (epoxy resin/block isocyanate <50 is preferred)
nIt is preferable that the EO content in the total resin composition is 15 to 20% or more.In the case of water stopping using water expansion, it is preferable to use it in a closed space, and it is not suitable for boat fishing. In the case of joint materials that have high water expansion, there is a high possibility that the adhesive surface will peel off due to water expansion and pop out from the joint. Therefore, for such applications, wet surface adhesion and flexibility are important. Emphasis should be placed on epoxy resin/blocked isocyanate = 20-60, and the EO content in the total resin composition is 5-20.
% is a preferred range.

In addition, in the case of flooring applications, the hydroxyl equivalent of the polyether polyol is 200 to 1000, and the epoxy resin/block isocyanate = 30 to 80. EO in total resin composition
The content is preferably about 5 to 10%.

The preferred blending ratio of each component of the composition of the present invention is as follows.

■Epoxy resin/■Blocked isocyanate compound-9
0-10/10-90 (weight ratio)n preferably ■/■=
20-70/80-30 (weight ratio) n The blending ratio of the curing agent (■) is ■+■/■ = 100/60-4 (weight ratio)n preferably ■+■/■-100/30-6 ( weight ratio).

In addition to these essential ingredients, the composition according to the invention contains reactive diluents, non-reactive diluents and fillers, fillers and/or reinforcing agents, pigments, solvents, plasticizers, leveling agents, thixotropic agents. Suitable diluents, fillers, reinforcing agents, Examples of fillers and pigments. Monoglycidyl ether, DP
Old BP, xylene resin, benzyl alcohol, tetrahydrofurfuryl alcohol, allocizer, coal tar, bituminous materials such as bitumen, textile fibers, cellulose,
Glass fiber, synthetic fiber, asbestos fiber, boron fiber, carbon fiber, cellulose, polyethylene powder, clay, sand, rock, quartz powder, mineral silicates such as mica, asbestos powder, crushed shale, kaolin, aluminum hydroxide, powdered Oxide pigments such as chijik, gypsum, antimony trioxide, bentonite, silica aerogel, lithopone, barite, titanium dioxide, talc, calcium carbonate, carbon black, graphite, iron oxide, or aluminum or iron powder. metal powder.

Suitable solvents for the modification of the curable compositions mentioned 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 monobutyl ether.

Plasticizers suitable for modifying the curable compositions mentioned above include, for example, butyl-, dioctyl- and dinonyl esters of phthalic acid, tricresyl phosphate, tricylenyl phosphate and polypropylene glycol.

Leveling agents which may be added when the curable compositions described above are to be used, in particular for surface protection, include, for example, silicones, acetylbutylcellulose, polyvinyl acetates, waxes, stearates and the like.

The curable composition of the present invention can be prepared using a known mixing device (
It may be manufactured using a stirrer, kneader, roller, etc.).

〔Example〕

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

In addition, parts in the examples mean parts by weight.

Production Example 1 1000 parts of a bifunctional polyester with a molecular weight of 2000 and an oxyethylene group content of 50% obtained by randomly adding propylene oxide and ethylene oxide to propylene glycol and 250 parts of diphenylmethane diisocyanate (molecular weight 250) are stirred. 70°C in 21 four-bottle flasks equipped with a thermometer, a thermometer, and a nitrogen inlet tube.
After 5 hours of reaction, the isocyanate equivalent was 1250 (NC
A urethane prepolymer with an O content of 3.4% was obtained, followed by the addition of 108 parts of cresol (molecular weight = 108),
C. for 5 hours to obtain blocked isocyanate A in which the isocyanate group completely disappeared according to an infrared absorption spectrum (blocked isocyanate equivalent: 1360).

Production Example 2 Molecular weight 3000. obtained by randomly adding propylene oxide and ethylene oxide to glycerin.
Trifunctional polyester 2 with oxyethylene group content of 51%
2 with a molecular weight of 2000 and an oxyethylene group content of 80% obtained by randomly adding propylene oxide and ethylene oxide to 00 parts and propylene glycol.
80 parts of functional polyester and tolylene diisocyanate (
Molecular weight 174) 174 parts were reacted in the same manner as in Production Example 1, and the isocyanate equivalent was 1174 (NGO content 3.6%).
urethane prepolymer was obtained, and nonylphenol (
Molecular weight: 220) 242 parts were added and reacted in the same manner as in Production Example 1 to obtain blocked isocyanate compound B (blocked isocyanate equivalent = 1416).

Production Example 3 Oxyethylene group content of bifunctional polyether is 20%
Blocked isocyanate C was obtained in the same manner as in Example 1 except that.

Comparative production example Polypropylene glycol (molecular weight 2000) 100
0 parts and diphenylmethane diisocyanate (molecular weight 25
0) in a 2Il four-bottle flask equipped with a stirrer, thermometer and nitrogen inlet tube at 70°C for 5 hours to obtain an isocyanate equivalent of 1250 (NGO content 3.4
%) of the urethane prepolymer, followed by cresol (
108 parts of molecular weight 10B) were added, and the mixture was reacted at 70°C for 5 hours to obtain a blocked isocyanate compound whose isocyanate groups had completely disappeared according to an infrared absorption spectrum (blocked isocyanate equivalent: 1360).

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

The results are shown in Table 1.

(Note) Umbrella 1: Made by Shell, bisphenol A type liquid epoxy resin (epoxy equivalent: 190) Skewer 2: Made by Asahi Denka,
Side chain type flexible epoxy (note) umbrella l manufactured by Asahi Denka Kogyo ■, polyamine adduct manufactured by Mitsui Texaco ■ resin (epoxy equivalent: 330, viscosity (25"C):
40 ps) Umbrella 3 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane As is clear from Table 1, the present invention product 1-1.1-2.1
The performance of the cured products of No.-3 after 30 days was not significantly different from the initial performance, and it can be said that there is almost no change in physical property values over time. In comparison, for flexible epoxy/polyamide-based comparative product 1-4, there was a remarkable change in the initial physical properties and the physical properties after 30 days, indicating that curing was progressing.

Example 2 The compositions shown in Table 2 were cured and their physical properties were examined.

The results are shown in Table 2.

Example 3 The compositions shown in Table 3 were cured and their physical properties were investigated.

The water swelling rate indicates the % weight increase after immersing the cured product in tap water for 7 days.

In addition, for moist surface adhesive eel, the composition was applied to a concrete test piece that had been immersed in water for one day and sufficiently moistened, and the composition was cured for 7 days in a container with saturated steam, and the adhesion was determined by a cross-over test. Examined.

The water stop test was conducted using an apparatus as shown in FIG.

That is, rings (test pieces) with a cross-sectional area of 20 x 10 cm and an inner diameter of 220 cm/ll were cast and molded, and these rings were
was attached to a water stop pressure tester with two grooves on the stainless steel flange 2, a spacer 3 was inserted so that the groove interval between the upper and lower flanges 2 was 10cm/-, and after tightening with bolts 4, the test was carried out for 10 days. After immersing in tap water, 3k in a water stop pressure tester.
A water pressure of gf/d was applied to check for water leakage.

The results are shown in Table 3.

〔Effect of the invention〕

The effect of the present invention lies in the provision of a curable epoxy resin composition that has flexibility, wet surface adhesion, and water swelling properties.

In particular, the curable epoxy resin composition of the present invention not only has excellent flexibility at low temperatures, but also has adhesion to wet surfaces and water-stopping properties due to water-swellability by using a specific hydrophilic polyether polyol. It is expected to be widely used in civil engineering and construction applications such as joint materials and flooring materials.

[Brief explanation of drawings]

FIG. 1 is a schematic cross-sectional view of the soil water pressure tester used in the water stop test. 1: Ring (test piece) 2: Stainless steel flange 3: Varnish spacer 4: Bolt

Claims (1)

[Claims] As essential constituents, [1] an epoxy resin having an average of more than one adjacent epoxy group in the molecule, [2] a general formula R[(OR')_nOH]_p (where R
is a polyhydric alcohol residue: (OR')_n is an oxyethylene group or a polyoxyalkylene chain consisting of an oxyethylene group and an oxyalkylene group having an alkylene group having 3 to 4 carbon atoms; however, the proportion of oxyethylene groups is the molecular weight It accounts for 5 to 100% of the total. n is a number indicating the degree of polymerization of the oxyalkylene group and corresponds to a hydroxyl equivalent of 200 to 2500; p is a number from 2 to 8); or a mixture of two or more polyether polyols and polyisocyanate. A urethane bond-containing compound ([2]-a) with an isocyanate group content of 1 to 10% by weight and an average molecular weight of 600 to 10,000 obtained from and a compound having a monohydric phenolic hydroxyl group ([2]-b), The isocyanate group of the compound ([2]-a) is masked with the phenolic hydroxyl group of the compound ([2]-b) by reacting at an isocyanate group/phenolic hydroxyl group equivalent ratio of 1/1.0 to 1.5. 1. A curable composition comprising a blocked isocyanate compound obtained by: and [3] an active organic amine curing agent.