JPS6041099B2 - Coating resin composition - Google Patents

Description

[Detailed description of the invention] The present invention relates to a coating resin composition.

Conventionally, curable resins obtained by adding alkanolamines to general-purpose epoxy resins obtained by reacting bisphenol A and epichlorohydrin in the presence of alkali hydroxide and reacting with polyfunctional isocyanates have been used for coatings. It has been widely used as a plastic resin.

However, conventional curable resins have insufficient solubility of alkanolamine adducts in organic solvents, low compatibility with white tar (tars that do not have amine functional groups), and Since it had a serious drawback of poor contact resistance, its use as a paint was severely restricted.

An object of the present invention is to provide a curable resin composition for coating that has excellent solubility, compatibility, and contact resistance.

The coating resin composition of the present invention has as essential components:
Epoxy resin (1) having an average of more than one adjacent epoxy group in the molecule and xylene/phenol/formalin resin (0) having a phenolic hydroxyl group per equivalent of epoxy group in the epoxy resin (1). , the alkanolamine (W) is added to the modified epoxy resin (mountain) obtained by reacting the phenolic hydroxyl groups in the xylene/phenol-formalin resin (D) in a proportion smaller than 1 equivalent with the active hydrogen in (W). It is characterized by containing a curable resin ① obtained by reaction and an organic polycyanate [B} together with an organic solvent in such a manner that the atoms and the epoxy group in (m) are equivalent to each other.

The epoxy resin (1) having an average of more than one adjacent epoxy group in the molecule used in the present invention is a substituted or unsubstituted epoxy resin represented by the formula (in which Z is a hydrogen atom, a methyl group, or an ethyl group). An average of 1 glycidyl ether group in the molecule
Eboxy resin (1-1) having more than one substituted or unsubstituted glycidyl ester group represented by formula (in which Z is a hydrogen atom, methyl group, or ethyl group) in the molecule on average Epoxy resin (1-2), with an average of one N-substituted or unsubstituted 1,2-epoxypropyl group represented by the formula (in this), Z is a hydrogen atom, a methyl group, or an ethyl group in the molecule. It includes epoxy resins (1-3), etc., which have many types.

The epoxy resin (1-1) having more than one substituted or unsubstituted glycidyl ether group in the molecule is an epoxy resin obtained by glycidyl etherification of a phenolic hydroxyl group and a glycidyl ether group containing an alcoholic hydroxyl group. Preferred examples of such epoxy resins (1-1) include epoxy resins obtained by etherification, and preferred examples of such epoxy resins include polyhydric phenols having one or more aromatic nuclei or at least one aromatic nucleus. Polyglycidyl ether (1-1-1) of a polyhydric alcohol having an alicyclic nucleus, a polyhydric phenol having one or more aromatic nuclei, or at least one
Polyglycidyl ether (1-1-2) of an alcoholic hydroxyl compound obtained by an addition reaction between a polyhydric alcohol having alicyclic nuclei and an alkylene oxide having 2 to 4 carbon atoms; Examples include polyglycidyl ethers (1-1-3) of other aliphatic polyhydroxy compounds.

However, polyglycidyl ether (1-1-1) is
For example, a polyhydric phenol (A-1) having at least one aromatic nucleus or a polyhydric alcohol (A-2) having at least one aliphatic nucleus and epihalohydrin [b-] may be combined with a compound such as sodium hydroxide. Epoxy resins containing polyglycidyl ether as the main reaction product, such as those obtained by reaction in the presence of a basic catalyst or a reactive amount of a basic compound, by a conventional method, polyhydric resins having at least one aromatic nucleus. Phenol (A-1) or a polyhydric alcohol having at least one alicyclic nucleus (A-2) and an epihalohydrin value are prepared by a conventional method in the presence of a catalytic amount of an acidic catalyst such as trifluoride. An epoxy resin such as the one obtained by reacting the polyhalohydrin ether obtained by the reaction with a basic compound such as sodium hydroxide, or a polyhydric phenol (A-1) having at least one aromatic nucleus, or Polyhydric alcohol (A-2) having at least one alicyclic nucleus and epihalohydrin [
An epoxy resin such as that obtained by reacting a polyhalohydrin ether obtained by reacting b' with a basic compound such as sodium hydroxide in a conventional manner in the presence of a catalytic amount of a basic catalyst such as triethylamine. be.

Similarly, polyglycidyl ether (1-1-2) or polyglycidyl ether (1-1-3) refers to, for example, polyhydric phenol (A-1) having at least one aromatic nucleus or at least one A polyhydric alcohol having alicyclic nuclei (A
-2) and an alkylene oxide having 2 to 4 carbon atoms A rigid or aliphatic polyhydroxy compound (C) and epihalohydrin 'b' are combined into trifluoride shelving units. The main reaction product is a polyglycidyl ether such as that obtained by reacting a polyhalohydrin ether obtained by a conventional method with a basic compound such as sodium hydroxide in the presence of an acidic catalyst amount such as It is an epoxy resin containing as.

Furthermore, polyglycidyl ethers of alcoholic polyhydroxy compounds derived by the addition reaction of polyhydric alcohols having at least one alicyclic nucleus or alkylene oxides having 2 to 4 carbon atoms are at least Hydrogenation of the aromatic nucleus of a polyglycidyl ether of an alcoholic polyhydroxy compound derived by an addition reaction between a polyhydric phenol having one aromatic nucleus or an alkylene oxide having 2 to 4 carbon atoms. It is also possible to obtain 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. At least 1
As the polyhydric phenol (A-1) having 1 aromatic nucleus, the polyhydric phenol (A-1) having 1 aromatic nucleus is
1-1) and polynuclear polyhydric phenol (A-1-2) having two or more aromatic nuclei.

Examples of such mononuclear polyhydric phenols (A-1-1) include resorcinol, 4,6-dichloro-o-resorcinol, hydroquinone, 2-furomohydroquinone, /guirocatechol, phloroglucinol, 1・5-
Examples include dihydroxynaphthalene, 2,7-dihydroxynaphthalene, and 2,6-dihydroxynaphthalene.

Examples of polynuclear polyhydric phenols (A-1-2) include those of the general formula [wherein ~] represents an aromatic divalent hydrocarbon such as a naphthylene group or a phenylene group, with a phenylene group being preferred for the purpose of the present invention.

Y' and Y, may be the same or different, and include a methyl group, n-propyl group, n-butyl group, n-hexyl group,
an alkyl group, preferably with up to 4 carbon atoms, such as the n-octyl group, or a halogen atom, such as a chlorine, bromine, iodine or fluorine atom, or a methoxy, methoxymethyl, ethoxy, ethoxycetyl group; Alkoxy groups such as n-butoxy and amyloxy are preferably alkoxy groups having up to 4 carbon atoms. When a substituent other than a hydroxyl group is present on either or both of the above-mentioned aromatic divalent hydrocarbon groups, these substituents may be the same or different. m and z are integers having values ranging from 0 (zero) to a maximum value corresponding to the number of hydrogen atoms in the aromatic ring (Ar) that can be substituted by a substituent, and can be the same or different values. R, for example, −○−,
1S-, 1SO-, 1S02- or alkylene groups such as methylene group, ethylene group, trimethylene group, tetramethylene group, bentamethylene group, hexamethylene group, 2-ethylhexamethylene group, octamethylene group, nonamethylene group, decamethylene group or alkylidene group, such as ethylidene group, propylidene group,
isopropylidene group, isobutylidene group, amylidene group, isoamylidene group, 1-phenylethylidene group or cycloaliphatic group such as 1,4-cyclohexylene group, 1.
3-cyclohexylene group, cyclohexylidene group or halogenated alkylidene group or halogenated alkylidene group or halogenated cycloaliphatic group or alkoxy- and aryloxy-substituted alkylidene group or alkoxy - and aryloxy-substituted alkylene groups or alkoxy- and aryloxy-substituted cycloaliphatic groups such as methoxymethylene group, ethoxymethylene group, ethoxychetylene group, 2-ethoxytrimethylene group, 3-ethoxybentamethylene group, 1・4-(2-toxycyclohexane) group, phenoxyshetylene group, 2-phenoxytrimethylene group, 1
・3-(2-phenoxycyclohexane) group or aryl-substituted alkylene group such as phenylethylene group, 2-phenyltrimethylene group, 1,7-phenylbentamethylene group, 2-phenyldecamethylene group or aromatic Group groups such as phenylene, naphthylene or halogenated aromatic groups such as 1,4-(2-chlorophenylene), 1,4-(2-pheorphenylene) or alkoxy- and aryloxy-substituted aromatics Group groups such as 1,4-(2-methoxyphenylene) group, 1,4-(2-methoxyphenylene) group,
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 group, 1,4-(21n dodecylphenylene) group, group represented by the formula (R is a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms), a group represented by the formula (wherein R2 is a hydrogen atom) or a divalent group such as a divalent hydrocarbon group such as a hydrocarbon group which may be substituted with a hydroxyl group or an epoxy group, or R is a saturated group represented by the formula, and q is 0 or 1. It is a polynuclear dihydric phenol represented by

Examples of such dihydric phenols may also be a ring fused to one of the Ar groups, as in the case of the compounds commonly represented by trade names, or R, may be a polyethoxy group, poly It can also be a polyalkoxy group, such as propoxy, polythioethoxy, polybutoxy, polyphenylethoxy, or R, such as polydimethylsiloxy, polydiphenylsiloxy, polymethylphenylsiloxy, etc. can be a group containing a silicon atom,
Or R is an aromatic group, a tertiary amino group, an ether bond,
There are polynuclear dihydric phenols represented by a carbonyl group or two or more alkylene or alkylidene groups separated by a sulfur or sulfur-containing bond such as a sulfoxide.

Particularly preferred polynuclear dihydric phenols are:
General formula (wherein, Y' and Y have the same meaning as in the above formula '1}, m and z have a value of 0 to 4, and R preferably represents an alkylene having 1 to 3 carbon atoms. 2,2-bis(4-hydroxyphenyl)propane, 2,4-dihydroxydiphenylmethane, pis(2-hydroxyphenyl)methane, bis(4-hydroxyphenyl), referred to as group or alkylidene group or formula bisphenol A Methane, bis(4-hydroxy-2,6-dimethyl-3-methoxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 1,2-bis(4-hydroxyphenyl)ethane, 1.1-pis (4-hydroxy-2-chlorophenyl)ethane, 1,1-bis(3,5-dimethyl-4-hydroxyphenyl)ethane, 1.3-pis(
3-methyl-4-hydroxyphenyl)propane, 2.
2-bis(3,5-dichloro-4-hydroxyphenyl)propane, 2,2-pis(3,5-dibromo-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-pis(4-hydroxynaphthyl)propane, 2,2- Bis(4-hydroxyphenyl)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(phenyl)propane, such as 2,2-pis(4-hydroxyphenyl)-1-phenylpropane.
hydroxyphenyl)alkane or 4,4'-dihydroxybiphenyl, 4,4'-dihydroxyoctachlorobiphenyl, 2,2-dihydroxybiphenyl, 2.
Dihydres such as 4-dihydroxybiphenyl.

Xipiphenyl or bis(4-hydroxyphenyl) sulfone, 2,4'-dihydroxydiphenyl sulfone, chloro-2,4-dihydroxydiphenyl sulfone, 5-chloro-4,4-dihydroxydiphenyl sulfone, 3'-chloro-4,4 -di(hydroxyphenyl) sulfone such as -dihydroxydiphenyl sulfone or bis(4-hydroxyphenyl) ether, 4,3-(
or 4,2'- or 2,2-dihydroxydiphenyl)
Ether, 4,4'-dihydroxy-2,6-dimethyldiphenyl ether, bis(4-hydroxy-3-isobutylphenyl) ether, bis(4-hydroxy-3
(isopropylphenyl) ether, bis(4-hydroxy-3-chlorophenyl) ether, bis(4-hydroxy-3-fluorophenyl) ether, bis(4-hydroxy-3-fromphenyl) ether, bis(4-hydroxy-3-fluorophenyl) ether, bis(4-hydroxy-3-fluorophenyl) ether,
-hydroxynaphthyl) ether, bis(4-hydroxy-3-chlornaphthyl) ether, bis(2-hydroxyphenyl) ether, 4,4-dihydroxy-2.
Includes di(hydroxyphenyl) ethers such as 6-dimethoxydiphenyl ether, 4,4'-dihydroxy-2,5-ditoxyphenyl ether, and 1,1
-bis(4-hydroxyphenyl)-2-phenylethane, 1,3,3-trimethyl-1-(4-hydroxyphenyl)-6-hydroxyindan, 2,4-bis(p
-hydroxyphenyl)-4-methylbentane is also suitable. Furthermore, another preferred group of such polynuclear dihydric phenols is represented by the general formula (2), where R3 is a methyl or ethyl group, R2 is an alkylidene group having 1 to 9 carbon atoms or other alkylene group, p is 0 to 4), for example, 1.4-pis (4-hydroxybenzyl)
Benzene, 1,4-bis(4-hydroxybenzyl)tetramethylbenzene, 1,4-pis(4-hydroxybenzyl)tetraethylbenzene, 1,4-bis(p-hydroxycumyl)benzene, 1,3-bis(p -hydroxycumyl)benzene and the like.

Other polynuclear polyhydric phenols (A-1-2) include, for example, 1,1,2,2-tetrakis (4
-Hydroxyphenyl)ethane, initial condensates of phenols and carbonyl compounds (e.g. phenol resin initial condensates, condensation reaction products of phenol and acrolein, condensation reaction products of phenol and glyoxal, phenol and pentanediallyl) condensation reaction products of resorcinol and acetone, xylene-phenol-formalin initial condensates), condensation reaction products of phenols and polychloromethylated aromatic compounds (e.g. phenol and bischloromethylxylene) condensation reaction products).

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

A preferable example of the mononuclear polyhydric alcohol (A-2-1) has the general formula HO-(R,)n-A-(R3)m-
OH (In the formula, A is a cyclohexane residue, preferably an alkyl group such as a methyl group, n-propyl group, n-butyl group, n-hexyl group, or n-octyl group)
Alkyl groups or halogen atoms, i.e. chlorine, bromine or fluorine atoms, or alkoxy groups such as methoxy, methoxymethyl, ethoxy, ethoxyethyl, n-butoxy, amyloxy, preferably up to 4 carbon atoms; It may or may not be substituted with an alkoxy group having 1 or more carbon atoms, but from the viewpoint of flame resistance, halogen substitution or no substitution is preferable.

R and R3 may be the same or different and may be alkylene groups such as methylene, n-propylene, n-butylene, n-hexylene, n-octylene, preferably alkylene having up to 6 carbon atoms. is the basis,
n and m are 0 or 1, preferably 0), such as 1,4-cyclohexanediol, 2-chloro-1,4-cyclohexanediol, 1・3
-cyclohexanediol, substituted or unsubstituted cyclohexanediol, such as 2-methyl-1,4-cyclohexanediol, and 1,4
-dihydroxymethylcyclohexane, 2-chloro-1,4-dihyde.

oxymethylcyclohexane, 1,3-dihydroxymethylcyclohexane, 1,4-dihydroxyethylcyclohexane, 1,3-dihydroxyethylcyclohexane, 1,4-dihydroxypropylcyclohexane, 1.
Substituted or unsubstituted dihydres such as 4-dihydroxybutylcyclohexane.

There is xyalkylcyclohexane. Furthermore, other mononuclear polyhydric alcohols having one alicyclic residue include 1.
3-cyclobentanediol, 1,3-cyclobentanediol, 1,4-cyclohef.

Tanediol, 1,4-cyclobentanediol, 1,5-perhydronaphthalenediol, 1,3-dihydroxy-2,2,4,4-tetramethylcyclobutane, 2,6-dihydroxy-decahydronaphthalene, 2.
Other substituted or unsubstituted cycloalkyl polyols such as 7-dihydroxy-decahydronaphthalene, 115-dihydroxy-decahydronaphthalene, and 1,3-dihydroxymethylcyclobentane, 1,4-dihydroxymethylcycloheptane, 2,6-bis (Hydroxymethyl)-1decahydronaphthalene, 2,7-bis(hydroxymethyl)-1decahydronaphthalene, 1,5-bis(hydroxymethyl)-decahydronaphthalene, 1,4-pis(hydroxymethyl)-1decahydronaphthalene, 1・
4-bis(hydroxymethyl)-bicyclo [2.2.2
]Octane, other substituted or unsubstituted polyhydroxyalkylcycloalkanes such as dimethyloltricyclodecane.

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

In addition, as an example of polynuclear polyhydric alcohol (A-2-2), general formula: day0(R,)n-(A,)k-[(R2)j
-(A2),]i-(R3)m-OH{3}[this]
, and A2 are monocyclic or polycyclic divalent alicyclic hydrocarbon residues, preferably an alkyl group such as a methyl group, n-propyl group, n-butyl group, n-hexyl group, or n-octyl group, preferably up to 4 Alkyl groups or halogen atoms, i.e. chlorine, bromine or fluorine atoms, or alkoxy groups such as methoxy, methoxymethyl, ethoxy, ethoxyethyl, n-butoxy, amyloxy, preferably up to 4 carbon atoms; It may or may not be substituted with an alkoxy group having 5 carbon atoms, but from the viewpoint of flame resistance, halogen substitution or no substitution is preferable.

Although k and 1 are 0 or 1, both k and 1 are never 0.

R2 is, for example, -○-, -S-, -SO-, -S02-, or an alkylene group, such as a methylene group,
Ethylene group, trimethylene group, isopropylene group, tetramethylene group, bentamethylene group, hexamethylene group,
2-ethylhexamethylene group, octamethylene group, nonamethylene group, decamethylene group or alkylidene group such as ethylidene, bropylidene group, isopropylidene group, isobutylidene group, amylidene group, isoamylidene 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 halogenation cycloaliphatic groups substituted with alkoxy and aryloxy, or alkylidene groups substituted with alkoxy and aryloxy, or alkylene groups substituted with alkoxy and aryloxy, or cycloaliphatic groups substituted with alkoxy and aryloxy, such as methoxymethylene groups, ethoxymethylene groups, Ethoxyshetylene group, 2-ethoxytrimethylene group, 3-ethoxybentamethylene group, 1,4-(2-toxycyclohexane) group, phenoxyshethylene group, 2-phenoxytrimethylene group, 1
・3-(2-phenoxycyclohexane) group or alkylene group such as phenylethylene group, 2-phenyltrimethylene group, 1-phenylbentamethylene group, 2-phenyldecamethylene group or aromatic group such as phenylene group, naphthylene group or Halogenated aromatic groups such as 1,4-(2-chlorophenylene), 1,4-(2-bromphenylene), 1,4-(2-fluorophenyletho), or alkoxy and aryloxy Substituted aromatic groups such as 1.4-(2-methoxyphenylene) group, 1.4-(2-ethoxyphenylene) group, 1.4-(2-n-propoxyphenylene) group, 1.
4-(2-phenoxyphenylene) group or alkyl-substituted aromatic group such as 1.4-(2-methylphenylene) group, 1.4-(2-ethylphenylene) group, 1.
4-(2-n-propylphenylene) group, 1,4-(2
R2 is a divalent group such as a divalent hydrocarbon group such as 1-n-butylphenylene) group, 1.4-1(2-n-dodecylphenylene) group, or R2 is, for example, in the case of a compound represented by the formula Alternatively, R2 can be a ring fused to one of the alicyclic residues, as in Alternatively, R2 can be a group containing a tertiary element, such as a polydimethylsiloxy group, a polydiphenylsiloxy group, a polymethylphenylsiloxy group, or R2 can be a tertiary aromatic ring group. It can be an amino group, an ether bond, a carbonyl group, or two or more alkylene groups or alkylidene groups separated by a bond containing sulfur such as sulfur or sulfoxide, but from the viewpoint of heat resistance etc., methylene group, ethylene group group, preferably an isopropylene group.

j is 0 or 1. R and R3 may be the same or different, for example an alkyl group such as methyl, n-propyl, n-butyl, n-hexyl, n-octyl, preferably an alkyl group having up to 6 carbon atoms. n and m are 0 or 1, preferably 0.

1 is a number greater than or equal to 0, preferably 0 or 1].

Particularly preferable polynuclear polyhydric alcohols (A-2-2) have the general formula: HO-A, 1(R2)j-n-O
It is a polynuclear dihydric alcohol represented by H (3-1) (where A, , A2, and R2i are the same as defined in the general formula above).

Preferred examples of polynuclear dihydric alcohols include, for example, 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-hydroxycyclohexylmethane).

hexyl)-methane, bis-(4-hydroxycyclohexyl)-methane, bis-(4-hydroxy-2,6-
Dimethyl-3-toxycyclohexyl)-methane, 1
・1-bis(4-hydroxycyclohexyl)-ethane, 1,1-bis(4-hydroxycyclohexyl)propane, 1.1-bis(4-hydroxycyclohexyl)butane, 1,1-bis(4-hydroxycyclohexyl)pentane, 2・2-pis(4-hydroxycyclohexyl)butane, 2,2-bis(4-hydroxycyclohexyl)pentane, 3,3-bis(4-hydroxycyclohexyl)-bentane, 2,2-bis(4-hydroxycyclohexyl)-hebutane, bis -(4-hydroxycyclohexyl)-phenylmethane, bis(
4-hydroxycyclohexyl)-cyclohexylmethane, 1.2-pis(4-hydroxycyclohexyl)
-1,2-bis-(phenyl)-propane, 2,2-bis-(4-hydroxycyclohexyl)-1-phenylpropane, 2,2-bis(4-hydroxy-3-methyl-cyclohexyl)propane, 2,2-bis (4-hydroxy-2-methyl-cyclohexyl)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-(3-isopropyl-4-hydroxycyclohexyl)-propane,
bis-(hydroxycycloalkyl) alkanes such as 2-isopropyl-4-hydroxycyclohexyl)propane, 2,2-bis-(4-hydroxyperhydronaphthyl)-propane or 4,4'-dihydroxybicyclohexane, 2,2-dihydroxy dihydroxybicycloalkanes such as picyclohexane, 2,4-dihydroxybicyclohexane, or bis-(4-hydroxycyclohexyl)-sulfone, 2,4-dihydroxydicyclohexylsulfone, chloro-2,4-dihydroxydicyclohexylsulfone, 5-chlor-4.
4-dihydroxydicyclohexyl sulfone, 3-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-isobutylcyclohexyl)-ether,
-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-hydro.xybicyclohexyl)-ether, 4,4'-dihydroxy-2,6-dimethoxydicyclohexyl ether, 4,4-dihydroxy-2,5
- Di(hydroxycycloalkyl) ethers such as diethoxydicyclohexyl ether, and 1.
1-bis(4-hydroxycyclohexyl)-2-phenylethane, 1,3,3-trimethyl-1-(4-hydroxycyclohexyl)-6-hydroxyindan,
2.4-bis-(p-hydroxycyclohexyl)-4
-Methylbentane is also suitable. Furthermore, another group of preferable polynuclear polyhydric alcohols (A-2-2) have the general formula: HO-A, -(R2)j-n-(R2)
j-A2-OH (3-2)(
In the formula, A,, A2, R2, j are the same as the definitions in the above general formula [311], and are two R2, two j, two A2
may have different shapes, for example, 1,4-bis(4-hydroxycyclohexylmel)
Cyclohexane, 1,4-bis(4-hydroxycyclohexylmethyl)tetramethylcyclohexyl, 1,4
-bis(4-hydroxyHO-R.-A,1(R2)j
-A2-R3 (in the formula A,, A2, R,, R2, R3,
i has the same definition as in the above general formula {31. ), substituted or unsubstituted dihydroxyalkylbicycloalkanes such as 4,4-dihydroxymethyl-bicyclohexane, and 1,2-bis(4-hydroxymethylcyclohexyl)ethane, 2,2-bis(4-hydroxy methylcyclohexyl)propane, 2
- Substituted or unsubstituted bis(hydro.xyalkylcycloalkyl) alkanes such as 3-bis(4-hydroxymethylcyclohexyl)butane and 2,3-dimethyl-2,3-bis(4-hydroxymethylcyclohexyl)butane. Therefore, the polyhydroxyl compound Tsukuda in this) refers to the polyhydric phenol (A-1) having at least one aromatic nucleus or the polyhydric alcohol (A-1) having at least one alicyclic nucleus. -2) and alkylene oxide with O
-RO bonded to the phenol residue or the alcohol residue through an ether bond obtained by reacting in the presence of a catalyst that promotes the reaction between the H group and the epoxy group;
H(R is an alkylene group derived from alkylene oxide) or (and)-(RO)nH(R is acyclohexylmethyl)tetraethylcyclohexane, 1.4-bis(p-hydroxycyclohexylisopropyl) ) diclohexane, 1,3-bis(p-hydroxycyclohexylisopropyl)cyclohexane, and the like.

Furthermore, another preferable group of polynuclear polyhydric alcohols (A-2-2) is one having the general formula: (3-3) alkylene oxide, which has an alkylene group derived from The chains may contain different alkylene groups.

n is a compound having an atomic group (2 or an integer of 2 or more indicating the number of polymerized oxyalkylene groups). In this case, the polyhydric phenol (A-1) or the polyhydric alcohol (
The ratio of A-2) and alkylene oxide is 1:1 (mol: mol) or more, but preferably the O of the polyhydric phenol (A-1) or the polyhydric alcohol (A-2)
The ratio of alkylene oxide to H group is 1:1-1
0, preferably 1:1 to 3 (equivalent: equivalent). child)
Examples of alkylene oxides include ethylene oxide, propylene oxide, and ethylene oxide, but those that generate side chains when reacting with the polyhydric phenol to form an ether bond are particularly preferred; Examples include propylene oxide, 1.2
-butylene oxide, 1,3-butylene oxide,
2,3-butylene oxide is preferred, particularly propylene oxide.

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

Furthermore, another group of preferable polyhydroxyl compounds include those having the general formula (wherein R,, R2, R
3 and p are the same as those in the above formula (1-2), and R
is an alkylene group having 2 to 4 carbon atoms, n is an alkylene group having 2 to 4 carbon atoms, and the ratio is 1 to 3.
It is a polyhydroxyl compound represented by

Furthermore, such a polyhydroxyl compound {8',
Another particularly preferred group has the general formula: ORn,
0-A, -(R2)j-n-○(RO)n2 days (in the formula,
A,, A2, R2, j are the same as those in the general formula (3-1), R is an alkylene group having 2 to 4 carbon atoms, n,
and & is a value of 1 to 3).

Furthermore, another group of preferable polyhydroxyl compounds {B} have the general formula: (OR)n,0-
A, one (R2) j-n- (R2) j-A2 one ○ (RO)
n2 days (wherein A., A2, R2, i represent the general formula (3)
-2), in which R is an alkylene group having 2 to 4 carbon atoms, n is a polyhydroxyl compound having a ratio of 1 to 3).

Particularly preferred among these mononuclear or polynuclear polyhydric alcohols {B} are alicyclic residues with 1 cyclohexane ring.
or two, among which dihydroxymethylcyclohexane, 2,2-bis-(4-hydro).

Preferred is oxycyclohexyl)-propane. Also, this)
Examples of aliphatic polyhydroxyl compounds that do not contain a nucleus include polyhydric alcohols such as ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, dibutylene glycol, glycerin, and bentaerystol; Polyhydroxyl compounds such as polyhydric alcohols or other active hydrogen-containing compounds (e.g. compounds with groups such as amino groups, carboxyl groups, thiohydroxyl groups, etc.) with alkylene oxides, polyether polyols, etc. Examples include compounds.

In addition, the above-mentioned epihalohydrin (b-) is represented by the general formula (
In this case, Z is a hydrogen atom, a methyl group, an ethyl group, and X' is a halogen atom. Bromohydrin, 1,2-epoxy 2-
Methyl-3-chloropropane, 1,2-epoxy 2-
Examples include ethyl-3-chloropropane.

The acidic catalyst that promotes the reaction between the above-mentioned epihalohydrin 'b} and the polyhydroxyl compound [B- or polyhydroxyl compound [C'] includes hydrogen trifluoride, stannic chloride,
Lewis acids such as zinc chloride and ferric chloride, derivatives exhibiting these activities (eg trifluoride-ether complex compounds), or mixtures thereof can be used.

Similarly, epihalohydrin'b} and polyhydric phenol (A
Basic catalysts that promote the reaction with -1) include alkali metal hydroxides (e.g. sodium hydroxide), alkali metal alcoholates (e.g. sodium ethylate), tertiary amine compounds (e.g. triethylamine, trietanolamine), quaternary ammonium compounds (e.g. tetramethylammoniumb.

(mide) or mixtures thereof can be used, so that the glycidyl ether is produced simultaneously with such reaction, or as a result of the reaction. Basic compounds that generate glycidyl ether by ring-closing hydrin ether through a dehydrohalogenation reaction include alkali metal hydroxides (e.g., sodium hydroxide), alkali metal salts of aluminate (e.g., sodium aluminate), etc. Used conveniently. Of course, these catalysts and basic compounds can be used as they are or as a solution in an appropriate inorganic or (and) organic solvent.

In addition, the epoxy resin (1-2) having on average one or more substituted or unsubstituted glycidyl ester groups in its molecule may include aliphatic polycarboxylic acids or aromatic polycarboxylic acids (e.g. phthalic acid, isophthalic acid, terephthalic acid). Acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, maleic acid, phthalic acid, itaconic acid,
In addition to succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dimer fatty acid, trimellitic acid, trimesic acid, pyromellitic acid, cyclobentanetetracarboxylic acid, these halogen-substituted compounds, these These include polyglycidyl esters (which may also include terminal carboxyl polyester oligomers obtained from polycarboxylic acids and polyhydric alcohols), such as epihalohydrin {b
It also includes epoxy resins such as those obtained by polymerizing glycidyl methacrylate synthesized from methacrylic acid and methacrylic acid. Examples of epoxy resins (1-3) having more than one N-substituted or unsubstituted 1,2-epoxypropyl group in the molecule include aromatic amines (e.g. aniline or alkyl substituted at the core). aniline having a group) and epihalohydrin [b} represented by the above general formula {4}, an initial condensate of an aromatic amine and an aldehyde (for example, an initial condensate of aniline-formaldehyde, an aniline-phenol Formaldehyde initial condensate, aniline-phenol-formaldehyde initial condensate) and epihalohydrin [b'].

Other epoxy resins include epoxidized linseed oil, epoxidized soybean oil, epoxidized safflower oil, epoxidized tung oil, epoxidized phenol oil, epoxidized dehydrated castor oil, epoxidized oiticica oil, epoxidized epoxidized fatty acids, epoxidized cyclic olefin compounds (e.g. vinylcyclohexene dioxide, 1-(1-methyl-1,2-epoxyethyl)) 3,4-epoxy-4-methylcyclohexane, 3
・4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy6-methylcyclohexanecarboxylate, bis(
3,4-epoxy 6-methylcyclohexylmethyl)
Adivate, dicyclobentene dioxide, dibentene dioxide, tetrahydroindene dioxide,
Or a compound in which these rings are bonded with a group as shown above as R in the general formula (A-2-1), and other Ar
alditeCY-175 (Ciba product name), etc.)
, epoxidized products of conjugated polymers (e.g. epoxidized polybutadiene, epoxidized styrene-butadiene copolymer, epoxidized acrylonitrile-styrene copolymer), epoxidized products of polymers containing unsaturated bonds (e.g. polypropylene) epoxides of polyisobutene, epoxides of polyisobutene), polyglycidyl ethers of polysiloxane, and epoxy resins containing heterocycles such as epoxy resins in which an epoxy group is bonded to the oxazolidinone ring via a carbon atom, diglycidyl ethers of furan, etc. ether compound, diglycidyl ether compound of dioxane, spiropylene
Examples thereof include diglycidyl etherified products of (m-dioxane), polyepoxy compounds obtained from imidazolines substituted with polyunsaturated alkenyl groups at the 2-position, triglycidyl isocyanurates, and the like.

In addition, conventionally known epoxy resins such as those described in "Production and Application of Epoxy Resins" (edited by Hiroshi Kakiuchi) may be used. Next, modified epoxy resin (m)
The xylene phenol formalin resin (b) having a phenolic hydroxyl group used in the production of is produced by reacting a xylene formalin resin obtained by condensing meta-xylene and formaldehyde under a strong acid with a monofunctional phenol or a polyfunctional phenol. On average 1 in the resulting molecule
Xylene phenol formalin resins containing more than 2 phenolic hydroxyl groups are preferred.

The above epoxy resin (1) and xylene phenol formalin resin (D) have less than 1 equivalent of phenolic hydroxyl group in the xylene phenol formalin resin (b) per 1 equivalent of epoxy group in the epoxy resin (1). The mixture is mixed with a catalyst (e.g., tertiary amine salt, quaternary ammonium salt, quaternary ammonium salt, Phosphonium salt, amine hydrochloride) was added and mixed, and 80
The reaction is carried out by heating to ~200qC, preferably 130-160q0.

The thus obtained modified epoxy resin (m) is reacted with an alkanolamine (W) to obtain the curable resin (2) of the present invention. As the alkanolamine (N), monoalkanolamine, dialkanolamine, etc. are used, and dialkanolamines such as diethanolamine, diisopro/gnolamine, dimethylethanolamine, methyljetanolamine, etc. are preferable.

The above modified epoxy resin (m) and alkanolamine (W
) is carried out by dissolving the modified epoxy resin (m) in an organic solvent such as xylene, heating it to a temperature of 60 to 9,000 and maintaining it, adding the alkanolamine (W), and heating it for 1 to 5 hours. Good.

The above alkanolamine (W) is added so that the active hydrogen atom in the alkanolamine (W) and the epoxy group in the modified epoxy resin (machi) are equivalent, and after the reaction is completed, the epoxy group in the modified epoxy resin (m) is The groups are linked to form a hydroxyl group.

The thus obtained curable resin film of the present invention is cured using an organic polyisocyanate leg containing two or more isocyanate groups as a curing agent. Polyisocyanate represented by the formula (n is an integer of 0 or 1 or more), 2.
Examples include 4-tolylene diisocyanate, 2,6-tolylene diisocyanate, xylene diisocyanate, hexamethylene diisocyanate, and an adduct of trimethylolpropane and tolylene diisocyanate (Coronate L).

The above-mentioned curable resin (1) and the organic polyisocyanate may be reacted in a conventional manner in such a manner that the respective hydroxyl groups and isocyanate groups are approximately equivalent in proportion.

The coating resin composition of the present invention containing the curable resin and organic polyisocyanate [B} obtained as described above together with an organic solvent may optionally contain other diluents, organic or inorganic pigments, etc. , dyes, fillers, and other additives.

The coating resin composition of the present invention has excellent solubility and compatibility with organic solvents, and therefore has good workability and excellent contact resistance, so it can be applied to a wide range of purposes.

The present invention will be explained below with reference to production examples and examples.

Production example 1 Bisphenol A diglycidyl ether 4
Add xylene/phenol-formalin resin 340 group (hydroxyl equivalent = 318) to 20 squares (epoxy equivalent = 180), and gradually heat to dissolve and raise the temperature to 100°C.

After that, 35g of trietanoamine was added as a catalyst,
While blowing in nitrogen gas, the temperature was further raised to 130°C and stirred for two periods. The epoxy equivalent of the obtained modified epoxy resin was 580. Xylene 3008 was added to 463 g of this modified epoxy resin and dissolved, and the temperature was maintained at 75q0. To this solution, 17 heads of diisopropanolamine were added over 3 minutes, and after the addition was completed, the temperature was raised to 80°C.
I worshiped the key for two hours. The obtained resin was a viscous liquid and had a hydroxyl equivalent of 305. Production Example 2 Xylene/phenol formalin resin 2908 (hydroxyl equivalent = 272) is gradually dissolved in Bisphere A/diglycidyl ether 480 (epoxy equivalent = 250) by heating, and the temperature is raised to 100 qo.

Then add 0.1r of 10% potassium hydroxide aqueous solution,
While blowing in nitrogen gas, the temperature was further increased to 150 oo, and the mixture was incubated for three periods. The epoxy equivalent of the obtained modified epoxy resin was 910.

Add 350 gr of xylene to this modified epoxy resin 770 and dissolve it at ? It was kept at 5°C. 8$r of diethanolamine was gradually added to this solution over 3 minutes.
After the addition was completed, the mixture was lit for 2 hours at 80 qo. The resulting resin was a viscous liquid with a hydroxyl equivalent of 295.

Examples 1-4, Comparative Examples 1-2 Coating films were obtained using the resins, polyisocyanates, and other components obtained in Production Examples 1-2.

The test results for the coating film are shown in Tables 1 and 2 below. Table I husband: Pisphenol A epoxy resin (epoxy equivalent = 21
Zalkanolamine adduct 2× of 00): Same as in Table 1

Claims (1)

[Claims] 1. As essential constituents, an epoxy resin (I) having an average of more than one adjacent epoxy group in the molecule and a xylene/phenol/formalin resin (II) having a phenolic hydroxyl group are added to the epoxy resin (I). Modified epoxy resin (III
), alkanolamine (IV) is further added so that the active hydrogen atoms in (IV) and the epoxy groups in (III) are equivalent, and the resulting curable resin (A) and organic polyisocyanate ( A coating resin composition characterized by containing B) together with an organic solvent.