JPS6395218A - Resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition, containing a specific polyether polyol resin and polyfunctional isocyanate compound, having excellent solubility in organic solvents, compatibility with bituminous materials (substitutes), corrosion resistance as well as flexibility and suitable as corrosion and heavy corrosion preventing coating materials. CONSTITUTION:A resin composition obtained by reacting a high-molecular weight epoxy resin, preferably having 1,000-4,000 epoxy equivalent prepared by reacting a substituted or unsubstituted glycidyl ether (having preferably 200-600 epoxy equivalent) of a polyhydric alcohol, e.g. ethylene glycol, etc., with a substituted or unsubstituted glycidyl ether (having preferably 170-300 epoxy equivalent) of a polyhydric phenol, preferably bisphenol A and a polyhydric phenol, preferably bisphenol A with a compound having a group reactive with epoxy groups, preferably N-methylalkanolamine, etc., to give a polyester polyol resin and blending the resultant resin with a polyfunctional isocyanate compound, e.g. toluene diisocyanate, etc.

Description

[Detailed Description of the Invention] (Industrial Application 1?) The non-invention relates to a resin composition for paint. In particular, the present invention provides a resin composition suitable for corrosion prevention and anticorrosion retention, which has excellent solvent solubility, compatibility with bituminous substances or their substitutes, and has corrosion resistance and flexibility. It is related to.

(Prior Art and Problems) Conventionally, as resin compositions for anticorrosion and heavy anticorrosion paints, dihydric phenol, II! A dihydric phenol such as bisphenol A is further reacted with 2-bis(4-hydromudiphenyl)glonomon (hereinafter referred to as bisphenol A) and epichlorohydrin, and the obtained low molecular weight Denko 4-oxy resin is further reacted with I. By chance, I got Shi Koubunshi Electric Works/dF Shiresin, and this? Those containing a lyisocyanate group-containing compound as a curing agent are generally used.

Although the polymer electrical engineering I xy resin has excellent physical properties such as corrosion resistance, water resistance, and adhesion, it has insufficient solubility in organic solvents and is incompatible with historical substances and/or their substitutes. Generally, the solubility is poor, and in reality it can only be used for specific retardant substances and/or their substitutes.Furthermore, the cured product is extremely hard and has poor flexibility, so when used as a paint, its use is limited. In order to improve these drawbacks of the above-mentioned Polymer Denko 4-xy resin, a glycidyl etherified product of the fulkylene oxide adduct of dihydric phenol was reacted with dihydric phenol. High molecular weight engineering z-? 4 obtained by further reacting a compound having a group that is reactive with the silica group in the resin with the cylindrical resin.
Reether-diol resin was considered (% 1989-
No. 7457), the Kobori ether 4 reol resin has been improved in its solubility in organic solvents, compatibility with backing substances and/or their substitutes, and flexibility of cured products. This has the serious drawback that the corrosion resistance inherent in epoxy resins is impaired. In addition, attempts have been made to blend this polyether polyol resin with the conventional high molecular weight engineered I-oxy resin described above to bring out the excellent properties of both, but as a result, corrosion resistance, solvent solubility, Both the compatibility with the backing material and/or its substitute and the flexibility of the cured product were insufficient.

(Means for solving the problem) The inventors of the present invention were faced with this situation and as a result of intensive study, they reacted a glycidyl ether of a polyhydric alcohol with a glycidyl nitrate polyhydric phenol of a polyhydric phenol. Using high molecular weight epoxy resin as a paste, the high molecular weight process/-? Is it possible to apply the remaining resin to the resin? By using a polyether polyol resin obtained by reacting a compound having a reactive group with an xyl group as the main resin and using a polyvalent isocyanate compound as a curing agent, it is possible to improve organic solvent solubility, bituminous substances and/or The present inventors have discovered that a coating resin composition can be obtained that has excellent compatibility with the present invention or its substitutes, and also has excellent corrosion resistance and flexibility of the coating film, and has completed the present invention.

That is, the present invention provides substituted or unsubstituted glycidyl ethers of polyhydric alcohols (a-1) (hereinafter referred to as polyhydric alcohol glycidyl ethers (a-1) and abbreviated as t), and substituted or unsubstituted glycidyl ethers of polyhydric phenols ( a-2) Reacting polyhydric phenol glycidyl ether (a-2)] with polyhydric phenol (a-3),
A polymer fl epoxy resin (A-1) is obtained, and a compound (A-2) having a group reactive with the epoxy group in the epoxy resin is obtained.
4-lyether deliol resin obtained by reacting (
A) and a polyvalent incyanate compound (B).

Polyhydric alcohol glycidyl ether (a
-1) Examples of polyhydric alcohols to be implanted include evapoethylene glycol, propylene glycol, I-lyethylene glycol, tripropylene glycol, butanediol, hexanediol, neopentyl glycol, trimethylpropane, glycerin, and water. In addition to polyhydric alcohols, which are generally referred to as additive bisphenol AS, examples include side adducts of polyhydric phenols with alkylene oxides.

The polyhydric phenol used in the above-mentioned polyhydric phenol adduct in alcohol has an aromatic nucleus in the molecule.
or more, and in which two or more hydroxyl groups are d-substituted on the aromatic nucleus, and examples thereof include mononuclear polyhydric phenols and polynuclear polyhydric phenols, but dihydric phenols are particularly preferred.

Such mononuclear polyhydric phenols include, for example, resorcinol, Hyde Kuchinone, C-locatechol, 70loglycinol, 1,5-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, and 2,6-dihydroxynaphthalene.

In addition, polynuclear polygfi phenol may be, for example, a compound of the general formula [wherein Ar is an aromatic divalent hydrocarbon such as a naphthylene group or a phenylene group, and for the purpose of the present invention, a phenylene group is preferable, and Y and Y2 are the same. - or may be different;
an alkyl group such as methyl, h-glol, n-tutyl, n-henosyl, n-octyl, an alkyl group preferably having up to 4 carbon atoms, or a halodane atom, i.e. A salt atom, a bromine atom, an iodine atom, or a fluorine atom, an alkoxy group such as an ethoxyethyl group, an ethoxyethyl group, an ethoxyethyl group, an ethoxyethyl group, an amyloxy group, preferably 4 or less. Al with carbon atoms:
2-? It is a group. If either or both of the above aromatic divalent hydrocarbon groups has a substituent other than the hydroxyl group, these substituents may be the same or different, k and t.
is an integer having a value from 0 (zero) to a maximum value corresponding to the number of hydrogen atoms of the aromatic It(Ar) that can be substituted by the t substituent, and can be the same or different values. R5 is, for example, -c-1-o-1-B-1-8O-1-so2-1
or an alkylene group, such as a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group,
Hexamethylene group, 2-ethyl naphthylene group, octamethylene group, nonamethylene group, decamethylene group, or alkylidene group, such as ethylidene group, globylidene group, isoprogylidene group, 7-mylidene group, 7-mylidene group, 7-mylidene group, 1-phenylethylidene group, or cycloaliphatic, such as 1,4-cyclohexylene group, 1,3-cyclohexylene group, cyclohexylidene group, or halodanated alkylene group, or a halogenated alkylidene group, or a halogenated cycloaliphatic group, or an alkylidene group substituted with C in alkoxy- and aryluo, or Al-: IdF and C-substituted in aryluo. 1 ．．
4- (2-methoxycyclohexane) group, phenoxyethylene group, 2-phenoxytrimethylene i, 1.3-
(2-phenoxycyclohexane) group, or alkylene group, such as phenylethylene group, 2-7enyltrimethylene group, 1,7-phenylpentamethylene group, 2-
phenyldecamethylene groups, or aromatic groups, such as phenylene groups, naphthylene groups, or halogenated aromatic groups, such as 1,4-(2-chlorophenylene);
group, 1.4-(2-fluorophenylene) group, or alkoxy and aryloxy t1-substituted aromatic group,
Example, ttfl, 4-(2-methoxyphenylene) group.

1.4-(2-ethoxyphenylene) group, 1,4-(
2-n-gropexyphenylene) group, l, 4-(2-phenoxyphenylene) group1. or an alkyl-substituted aromatic group, such as 1.4-(2-methylphenylene), 1.4-(2-ethylphenylene), 1.4
- (2-n-propylphenylene) group, 1.4- (
2-n-butylphenylene) group, 1.4- (2-n-
2, such as divalent hydrocarbon groups such as dodecylphenylene) groups.
or R5 can also be a ring fused to one of said Ar groups, as is the case for example in the compound of formula; or R5a/+7 ethoxy group, ? It can also be a 4-alco group, such as a cy group in lipropo, a cy group in I-lithioeth, a polytoxy group, a cy group in prephenyleth, or R6 can be, for example, a cy group in I-lydimethylsilo, a polydiphenylsilo group. Shi group? It can be a group containing a silicon atom, such as a trimethylphenylsiloxy group, or R1 can be an aromatic group, a tertiary-amino group, an ether bond, a car-el group, or a sulfur group, such as a sulfoxide group. two or more alkylene or alkylidene groups separated by a bond containing polynuclear polyhydric phenols.

Among such polynuclear polyhydric phenols, those having the general formula (wherein Y and Y2 have the same meanings as above, V and t' are integers of 0 to 4, and Hs/ is preferably a is 1-3
an alkylene group or an alkylidene group having 4 carbon atoms,
or a saturated group represented by the formula).

Examples of such 2@liphenols include 2s2-his(p-hy)'roxyphenyl)pro/benz, 2,4'-dihydroxydiphenylmethane, bis(2-hydroxyphenyl), commonly referred to by the trade names bisphenols. Methane, bis(4-hydroxyphenyl)methane, bis(4-
2,6-dimethyl-3-methane, diphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 2-bis(4-hydroxyphenyl)ethane, 1.1-bis(4- 2-chlorophenyl)ethane, 1,1-bis(3,5-dimethyl-4-hydroxyphenyl)ethane, 1,3-bis(3-methyl-
4- and diphenyl in doro) Furo/gun, 2.2-k
's(365-dichloro-4-hydroxyphenyl)clopane, 2,2-bis(3-7enyl-4-hydroxyphenyl)f/4-in, 2,2-bis(3-isopropyl-4-hydroxyphenyl) ) pro/mathane, 2,2-bis(2-isopropyl-4-hydroxyphenyl)gulon, 2,2-bis(4- and dinaphthyl)propane, 2,2-bis(4-hydroxyphenyl) ) intane, 3.3-bis(hydroxyphenyl)-entane,
2.2-bis(4-hydroxyphenyl)hebutane, bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)cyclohexylmethane, 1,2-bis(4-hydroxyphenyl)-1,2-bis (phenyl)piphenyl, 2,2-bis(4-hydroxyphenyl)-1-phenyl, bis(hydroxyphenyl)alkane, such as groin, or 4,4'-dihydroxypiphenyl, 2.2'-dihydroxybiphenyl,
2. 4'-dihydroxypiphenyl, or bis(4-hydroxyphenyl)
sulfone, 2,4'-dihydroxydiphenylsulfone, 2,4-dihydroxydiphenylsulfone,
3-chloro-L4'-'/hydroxydiphenylsulfone, di(hydroxyphenyl)sulfone, such as 3'-chloro-4,4'-dihydroxydiphenylsulfone, or bis(4-hydroxyphenyl)ether, 4.
3'-(or 4,2'- or 2,2'-dihydroxy-
diphenyl)ether, 4,4'-dihydroxy-2,
6-dimethyldiphenyl ether, bis(4- and di-3-isobutylphenyl) ether, bis(4-hydroxy-3-isochloropylphenyl) ether, bis(4-hydroxy-3-chlorophenyl) ether , bis(4-hydro-3-fluorophenyl) ether, bis(4-hydroxy-3-bromphenyl) ether, bis(4-hydroxynaphthyl) ether, bis(
3-chlornaphthyl in 4-hydroether, bis(cybiphenyl in 2-hydro)ether, cydiphenyl in 4,4'-dihydro-2,6-dimeth ether,
4.4'-1'Hydroxy-2,s-shed contains //(hydroxyphenyl)ethers such as sidiphenyl ether, and also includes 1,1-bis(4-hydroxyphenyl)-2-phenylethane, 1 .3.3-) dimethyl-
1,-(4-hydroxyphenyl)-6-hydroxyindan, 2,4-bis(p-hydroxyphenyl)-4
-Methylpentane is also suitable.

Furthermore, another group of preferable polynuclear polyhydric phenols has the general formula (wherein R5 is a methyl group or an ethyl group, and R4 is a carbon number 1
~Furu of 9? 92 N group or other alkylene group, j
is an integer from 0 to 4), such as 1,4-bis(4-hydroxybenzyl)benzene, 1,4-bis(4-human tetraxybenzyl)tetramethylbenzene, 1,4-bis(4
-Hydroxybenzyl)tetrae? /I/benzene, l
, 4-bis(p-human dicumyl)benzene, 1.3
-bis(p-hydroxycumyl)pensene and the like.

Other polynuclear polyhydric phenols include, for example, initial condensates of phenols and Cal-Nyl compounds (e.g., phenol resin initial charge, condensation reaction products of phenol and acrolein, condensation reaction products of phenol and glyoxol). , phenol (condensation reaction product of tannediallyl, condensation reaction product of resorcinol and 77 tons, xylene-phenol-formalin initial condensate), condensation product of phenols and polychloromethylated aromatic compounds (
Examples include synthetic acids of phenol and bischloromethylxylene).

Further, the alkylene oxide to be added to the polyhydric phenol is, for example, fullylene oxide having 2 to 4 carbon atoms, and preferable examples include ethylene oxide,
Examples include globylene oxide, butylene oxide, and mixtures thereof.

Therefore, the production of a fullylene oxide adduct of a polyhydric phenol is particularly effective when the polyhydric phenol and the fullylene oxide are reacted in the presence of an alkaline or acidic catalyst.

The ratio of the polyhydric phenol to the fullylene oxide is usually 1 to 10 alkylene oxides, preferably 1 to 3 alkylene oxides per hydroxyl group of the polyhydric phenol.

The polyhydric phenol constituting the polyhydric phenol (a-3) and polyhydric phenol glycidyl ether (a-2) used in the present invention may be the same as the polyhydric phenol used in the fullylene oxide adduct of the polyhydric phenol described above. Among them, bisphenols, bisphenol F, phenols such as lac and talesol nogelac are preferred, and IIItc bisphenol A is preferred.

The polyhydric alkyl glycidyl ether used in the present invention (
a-1) and polyhydric phenol glycysol ether (a-
2), for example, in the presence of an alkali hydroxide catalyst, a polyhydric alcohol or a polyhydric phenol is combined with one or more compounds selected from halogenohydrin, methylethylhalol/hydrin, and dihalogenohydrin. It is easily obtained by reaction.

Here, the examples of ebi bromohydrin, methyl enohydrin, and dihalogenohydrin include epichlorohydrin, ebi tetramohydrin, methyl ezochlor, dolino,
Examples include methylepic-concentrated mohydrin, dichlorohydrin, and dichlorohydrin, among which it is preferable to use methylepibromohydrin, dichlorohydrin, and methylepichlorohydrin.

Here, the reaction ratio between polyhydric alcohol or polyhydric phenol and one or more compounds selected from Ebihachi 1:lr nohydrin, methyl epichlorohydrin, and Shibahirogutuhydrin is 1 to 10% of the latter to 1 equivalent of the former. The epoxy equivalent of the glycidyl ether compound obtained is preferably the same as the polyhydric alcohol glycidyl ether (a
-1) is preferably 200 to 600, and polyhydric phenol glycidyl ether (a-2) is preferably 170 to 1.000.
is preferable, and 170 to 300 is particularly preferable.

Examples of the high molecular weight resin (A-1) used in the present invention include polyhydric alcohol glycidyl ether (a-
1) and polyhydric phenol glycysol ether (a-2) at a molar ratio (a-1)/(a-2) of 40/60 to 90/
10. It is preferably used in the range of 60/40 to 80/20, and the product obtained by adding polyhydric phenol (a-3) to this and reacting at 80 to 250°C in the presence of a catalyst is used. The epoxy equivalent is 500 to 6. O
OO is preferred, especially 1.000 to 4.00. OOO is particularly preferred.

In addition, the reaction between polyhydric alcohol glycidyl ether (a-1), polyhydric phenol glycidyl ether (a-2), and polyhydric phenol (a-3) is as described in (a-1) above.
Usually, the above (a-3) is added to a mixture of (a-2) and reacted, but (a-1) and (a-3) or (a-2) and (a-3 After starting the reaction with ), the remainder (a-2) or (a-1) may be added at any stage for further reaction.

In addition, the catalysts used for this reaction include caustic soda,
Inorganic alkalis such as caustic potash and soda carbonate; tertiary amines such as triethylamine, triethanolamine, dimethylamine, and zeridine; , 3 boron fluoride, aluminum chloride, 4 tin chloride, 4
Examples include Lewis acids such as titanium chloride.

Examples of the compound (A-2) having a group reactive with an epoxy group used in the present invention include a compound containing an amino group, a compound containing a phenol group, a compound containing a carmexyl group, etc. Use a mixture of two or more.

Examples of compounds containing an amino group include primary amines,
Examples include secondary amines, and among them, alkanolamines containing hydroxyl groups, particularly N-alkylalkanolamines, are preferred. Examples of primary amines include methylamine, ethylamine, and globilaine; examples of secondary amines include dibutylamine; and particularly preferred alkanolamines include ethanolamine, globilaine, and the like.
N-alkylalkanolamines include N-methylethanolamine, which is particularly preferred as N-alkylalkanolamine.

Luain, N-ethylethanolamine, N-7''a-biruethanolamine, N-inglovirethanolamine, N-1-thylethanolamine, N-methylglol
N-ethylglopanolamine, N-
Pushi Pilgro/Ue Noru 7 (n.

N-Inglobilgulo/#Nolamine, N-Butylg 4/4Nolamine% N-Methylinozolo/Nolamine, N-Ethylino f t2zqNolamine, N-
Examples include terpanolamine, N-butyl isoglobin/tetrapanolamine, N-butyl isoglobin/tetrapanolamine, and the like.

Further, examples of compounds containing a phenol group include monohydric phenol and 2(iiffiphenol).

Among them, monovalent 78nol is preferable, and examples of such a monovalent phenol include phenol, cresol, lii
+1 silenol, t-butylphenol and the like.

Examples of compounds containing a carboxyl group include monocaronic acid and carboxylic acid.

Among them, heptanocarboxylic acid is preferred, and examples of monocardic acid include glupionic acid and lactic acid.

Examples of dicarnic acids include maleic acid, adipic acid, ':1 uccinic acid, 7-talic acid, and isophthalic acid.

Tetrahydrophthalic acid etc. Among the compounds (A-2) having a group reactive with these epoxy groups,
Particularly preferred are N-alkylalkanol iso, and among these, N-methylethanolamine, N-ethylethanolamine, N-fvsvirethanolamine, and N-inglovirethanolamine are preferred because of their fast curing speed. In addition, when using the compound (A-2
) containing 20 to 100 N-alkylalkanolamines in
It is preferable to use the compound (A-1) in a proportion by weight of the high molecular weight epoxy resin (A-1) and the above compound (A-2) when obtaining the riether polyol resin (4). ) and the latter (A-
The equivalent blending ratio of the group reactive with the epoxy group in 2) is preferably 0.7 to 1.3, particularly preferably 0.9 to 1.1. For example, when a compound containing a phenol group or a xyl group is used, the reaction may be carried out at a temperature of 80 to 250°C in the presence of the same catalyst as mentioned above, or when a compound containing an amino group is used. If used, it can be carried out without a catalyst, for example at a temperature of 60 to 150°C.

Examples of polyvalent incyanate compounds used in the present invention include toluene diisocyanate, xylylene diisocyanate, crude diphenylmethane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate methyl ester, and trimethylol! Examples include a 3-mole toluene diincyanate adduct of Lonotan and a high molecular weight polyisocyanate (brepolymer) obtained therefrom.

The blending ratio of the polyvalent incyanate compound is such that the blending ratio of the water @ group equivalent and the incyanate group equivalent in the polyether polyol resin is 0.4 to 1.2. Preferably 0.7-1.0
A good ratio is such that

Coal tar is a bituminous substance that is usually added when the resin composition of the present invention is used as a paint.

Coal tar pitch, 4 cutback tars each.

Swollen charcoal, asphalt, etc. can be used.

Substitutes for bituminous substances include viscous substances, such as aromatic oil resins, coumaron resins, dioctyl phthalate and dibutyl phthalate, which are generally used as diluents, and other petroleum-based coals. Neutral oils with high Buddha points, such as those of the same type, can be used. The appropriate blending ratio of the bituminous substance and/or the substitute for the bituminous substance is 0.5 to 2 times the weight of the d-riether polyol resin.

Incidentally, various curing catalysts, fillers, diluents, dehydrating agents, resins, etc. can be added to the composition of the present invention as required.

(Effects of the Invention) The resin composition of the present invention has the advantage that it has good solubility in organic solvents, compatibility with bituminous substances or their substitutes, good castability of cured products, and excellent corrosion resistance of cured products. There is.

Using this, nine paints are used in the corrosion protection and heavy corrosion protection fields, such as ships, vehicle widths, bridges, large structures such as steel frames, water supply and sewage systems, sea water I/drainage pipes, etc., as well as household electrical appliances. It can be suitably used for retaining and handling instruments, steel shelves, mortar contact structures, etc.

(Example) The present invention will be explained in more detail below using manufacturing examples, working examples, and comparative examples. Note that the parts in the example are based on the heavy f standard.

Production Example 1 (Production of diether 4-liol resin) Glycidyl ether (epoxy fi371) of bisphenol propylene oxide adduct obtained by adding dipropylene oxide 4 (4) per mole of bisphenol and reacting with epichlorohydrin to convert it into glycidyl ether. 8
5.5 parts and Ebicuron 850 [Dainippon Ink Chemical Industry (
Bisphenol glycidyl ether manufactured by Co., Ltd., epoxy equivalent 188) 14.5 parts, and bisphenol A 27
．． 5 parts were reacted with sodium hydroxide as a catalyst at 200°C for 10 hours with continuous heating and stirring to obtain a high molecular weight epoxy resin (g2.05 o per epoxy), which was further added with N
-Process 5 parts of methylethanolamine.

The mixture was stirred and reacted at 110° C. for 3 hours to obtain /reether polyol resin (1) (water altl white group 356).

100 parts of toluene or xylene was added to 100 parts of the obtained 9-riether polyol resin (1) to check the solubility, and it was found that it could be easily dissolved.

Production example 2 (same as above) 9 parts in place of 5 parts of N-methylethanolamine.

The same procedure as Production Example 1 was carried out except that 6.2 parts of phenol was added and the reaction was carried out by heating and stirring at 200° C. for 4 hours.

Polyether polyol resin (■) (hydroxyl group-i43
6) was obtained. The obtained polyether 4 reol resin (
II) 100 parts of toluene or medium silane was added to 100 parts to check the solubility, and it was found that it could be easily dissolved.

Production Example 3 (same as above) Evicron 86 (instead of 14.5 parts of Epicron 850)
0 [Dainippon Ink & Chemicals (TL') p-bisphenol A glycidyl ether, epoxy equivalent 250)
Polymer Denko 4 xy resin (epoxy equivalent (J-2,130)) was obtained in the same manner as in Production Example 1 except that 19.3 parts was used.
Then, in the same manner, I-reather polyol resin (to) (
Hydroxyl group j1369) was obtained.

Got it! We tested the solubility by adding 100 parts of toluene or xylene to 100 parts of riether polyol resin, and it was found that it could be easily dissolved.

Production Example 4 (same as above) Using 35.1 parts of glycidyl ether of neopentyl glycol (epoxy equivalent: 155) instead of 85.5 parts of glycysol ether (epoxy equivalent: 1371) of bisphenol A 7'0 pyrene oxide adduct, Polymer was prepared in the same manner as Production Example 1 except that the amount of bisphenol A used was changed from 27.5 parts to 35.1 parts! Ether I lyol resin ω was obtained in the same manner except that 72.3 parts of N-methyl ethanol was further added to this epoxy resin (i 2,800 per epoxy).

Add 100 parts of toluene or xylene to 0.100 parts of the obtained ft--reather polyol resin. i! ! I checked the dissolution properties and found that it could be easily dissolved.

Production Example 5 (same as above) Bisphenol A 51.
Add 5 parts and heat to 200°C using sodium hydroxide as a catalyst.
The reaction was continued by heating and stirring for 10 hours, and the
An oxy resin (epoxy weight: 1!: 2,000) was obtained, and to this was further added 76 parts of N-methyl ethanol apolymer to give 11
The reaction mixture was stirred at 0° C. for 3 hours to obtain polyether polyol resin (V) (hydroxyl equivalent: 258). 100 parts of the obtained polyether polyol resin (up to 100 parts) did not dissolve even when 100 parts of toluene or xylene was added, and it was necessary to add a ketone or alfur solvent to dissolve it.

Production Example 6 (same as above) Glycidyl ether of bisphenol-propylene oxide adduct (epoxy 1371), which was obtained by adding 4 moles of dipropylene oxide to bisphenol A1 and reacting with p-ruhydrin to convert it into glycidyl ether.
Add 23.5 parts of bisphenol A to 100 parts,
The reaction was carried out by heating at 200°C for 10 hours using sodium hydroxide as a catalyst (continuous stirring) to obtain a high molecular weight engineering I resin (F1?Φ equivalent weight 2030), which was further mixed with N-methyl ethanol 5 1 part and heated at 110℃ for 3 hours (・1
Press to react, / rietherboliol resin (b) (
Hydroxyl equivalent (383) was obtained, and 100 parts of the obtained polyether polyol resin (up to) was added with 10 parts of toluene or xylene.
I added 0 parts to check the dissolution properties, but it was easy to dissolve and there were no holes.

Production Example 7 (same as above) One ether polyol of Production Example 5 1eIJ11 (to)
50 parts and 50 parts of the polyether polyol resin (b) of Production Example 6 were mixed, and 1! ! ! Liether I Liol resin (■) (5130 g based on hydroxyl group) was obtained. 100 parts of toluene or xylene was added to 100 parts of the obtained one-etheruriol resin (■) to check its solubility.

It was not completely dissolved and it was necessary to add a portion of a tonne or alcohol solvent.

Examples 1-8 and Comparative Examples 1-. 6 Nine polyethers I Rio obtained in Production Examples 1 to 7, 11/
Using resins (I) to (■), coating resin compositions having the compositions shown in Mending-1 and Table-2 were prepared, and n! Apply with a rusted steel plate doctor grate so that the film thickness after drying is 200μm,
In addition to measuring the curing time at 10°C (time until a person can walk on it).

The corrosion resistance and flexibility of the coating film after being allowed to stand at 10° C. for one week after being clothed was examined.

The coating resin compositions of Examples 1 to 8 all showed excellent corrosion resistance and flexibility, but Comparative Examples 1 and 4 had excellent corrosion resistance but poor disposability, and Comparative Examples 2-3・5 and 6
had excellent flexibility but poor corrosion resistance.

Comparing Examples 1 to 8, Examples 1 and 3 using N-methylethanolamine were preferable because of their fast curing speed. The measurement results are shown in Shishi-1 and 6-2.

Claims (1)

[Claims] Substituted or unsubstituted glycidyl ethers of polyhydric alcohols (
a-1), substituted or unsubstituted glycidyl ether of polyhydric phenol (a-2), and polyhydric phenol (a-3) to obtain a high molecular weight epoxy resin (A-1), which A polyether polyol resin (A) obtained by further reacting a compound (A-2) having a group reactive with an epoxy group, and a polyvalent isocyanate compound (B)
A resin composition comprising: