JPH028626B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a coating resin composition. In particular, the present invention relates to a coating resin composition that has excellent corrosion resistance, water resistance, other adhesion properties, and mechanical properties for forming coating films. Conventionally, as a coating composition, a low molecular weight epoxy resin obtained from a divalent phenol, particularly 2,2-bis(4-hydroxyphenyl)propane (hereinafter referred to as bisphenol A) and epichlorohydrin is further reacted with a divalent phenol. In general, a high molecular weight epoxy resin is obtained by this process, and a polyol resin is obtained by further adding amines, and this is blended with a polyisocyanate group-containing compound as a curing agent. However, although polyols based on the above-mentioned high molecular weight epoxy resins are known to have excellent physical properties, they have insufficient solubility in organic solvents, and the cured products are extremely hard and lack flexibility. Because of these drawbacks, there were significant restrictions on its use when used as paint. The purpose of the present invention is to provide a coating resin composition that eliminates the above-mentioned drawbacks and has excellent properties, and the present inventors arrived at the present invention while proceeding with various studies for such purpose. did. That is, the coating resin composition of the present invention is obtained by reacting a substituted or unsubstituted glycidyl ether of an alkylene oxide adduct of divalent phenol with a dicarboxylic acid to obtain a high molecular weight epoxy resin, which is further reacted with an epoxy group. It is characterized by containing a polyether polyol resin obtained by reacting a compound having a group having a property, a compound having more than one isocyanate group, and a bituminous substance and/or its substitute. be. Here, divalent phenol refers to a phenol having one or more aromatic nuclei in the molecule and in which the aromatic nucleus is substituted with two hydroxyl groups, and includes mononuclear divalent phenol and polynuclear divalent phenol. phenols. Examples of such mononuclear divalent phenols include resorcinol, hydroquinone, pyrocatechol, phloroglycinol, 1,5-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, and 2,6-dihydroxynaphthalene. In addition, as an example of polynuclear divalent phenol, the general formula [Wherein, Ar is an aromatic divalent hydrocarbon such as a naphthylene group or a phenylene group, and a phenylene group is preferred for the purpose of the present invention. Y′ and Y ₁ may be the same or different, and may be a methyl group, n-propyl group, n
- an alkyl group, preferably with up to 4 carbon atoms, such as butyl, n-hexyl, n-octyl, or a halogen atom, i.e. chlorine, bromine, iodine or fluorine; Alkoxy groups preferably have up to 4 carbon atoms, such as methoxy, methoxymethyl, ethoxyethyl, n-butoxy, amyloxy. 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 0 corresponding to the number of hydrogen atoms in the aromatic ring (Ar) that can be substituted with a substituent.
An integer with a value from (zero) to a maximum value, which can be the same or different values. R ₁ is for example

[Formula] -O-, -S-, -SO-, -SO ₂ - or alkylene group such as methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, 2-ethylhexamethylene group , octamethylene group, nonamethylene group, decamethylene group or alkylidene group such as ethylidene group, propylidene group, isopropylidene group, isobutylidene group, amylidene group, isoamylidene group, 1-phenylethylidene group or cycloaliphatic group such as 1, 4-cyclohexylene group,
1,3-cyclohexylene group, cyclohexylidene group, halogenated alkylene group, halogenated alkylidene group, halogenated cycloaliphatic group, or alkoxy- and aryloxy- Substituted alkylidene groups or alkoxy- and aryloxy-substituted alkylene groups or alkoxy- and aryloxy-substituted cycloaliphatic groups such as methoxymethylene, ethoxymethylene, ethoxyethylene, 2- ethoxytrimethylene group,
3-ethoxypentamethylene group, 1,4-(2-
methoxycyclohexane) group, phenoxyethylene group, 2-phenoxytrimethylene group, 1,3-
(2-phenoxycyclohexane) group or alkylene group such as phenylethylene group, 2-phenyltrimethylene group, 1,7-phenylpentamethylene group, 2-phenyldecamethylene group or aromatic group groups such as phenylene, naphthylene or halogenated aromatic groups such as 1,4-
(2-chlorophenylene) 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 group or an alkyl-substituted aromatic group such as 1,4-(2-methylenephenylene 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 R ₁ is a divalent group such as a divalent hydrocarbon group such as It can also be a ring fused to one of the Ar groups as in the case of the compound represented by
R ₁ can also be a polyalkoxy group such as polyethoxy, polypropoxy, polythioethoxy, polybutoxy, polyphenylethoxy, or R ₁ can be e.g. polydimethylsiloxy, polydiphenylsiloxy group, a group containing a silicon atom such as a polymethylphenylsiloxy group, or R ₁ can be an aromatic ring, a tertiary amino group, an ether bond, a carbonyl group or a sulfur-containing group such as sulfur or sulfoxide. polynuclear dihydric phenols, which can be two or more alkylene or alkylidene groups separated by a bond containing them. Among these polynuclear divalent phenols, particularly preferred are those of the general formula (In the formula, Y′ and Y ₁ have the same meanings as above, m
and z are values from 0 to 4, and R ₁ is preferably 1
an alkylene or alkylidene group or formula with ~3 carbon atoms

【formula】

【formula】

A polynuclear 2 represented by [Formula] which is a saturated group represented by
It is a valent phenol. Examples of such dihydric phenols include 2,2-bis(p-hydroxyphenyl)propane, 2,4'-dihydroxydiphenylmethane, and bis(2-hydroxyphenyl), commonly referred to by the trade name bisphenol A. 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)ethane enyl)propane, 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane, 2,2-bis(3
-phenyl-4-hydroxyphenyl)propane, 2,2-bis(3-isopropyl-4-hydroxyphenyl)propane, 2,2-bis(2-
Isopropyl-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxynaphthyl)propane, 2,2-bis(4-hydroxyphenyl)pentane, 3,3-bis(hydroxyphenyl)pentane, 2 , 2-bis(4-hydroxyphenyl)heptane, bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)cyclohexylmethane, 1,2-bis(4-hydroxyphenyl)-1,2 -bis(phenyl)propane, 2,2-bis(4-hydroxyphenyl)
- bis(hydroxyphenyl) alkanes such as 1-phenylpropane or dihydroxybiphenyl such as 4,4'-dihydroxybiphenyl, 2,2'-dihydroxybiphenyl, 2,4'-dihydroxybiphenyl; enyl or bis(4-hydroxyphenyl)sulfone, 2,4'-dihydroxydiphenylsulfone, chloro-2,4-dihydroxydiphenylsulfone, 5-chloro-4,4'-dihydroxydiphenylsulfone, 3 ′-chlor-
Di(hydroxyphenyl) sulfones such as 4,4'-dihydroxydiphenyl sulfone or bis(4-hydroxyphenyl) ether, 4,3'-
(or 4,2'- or 2,2'-dihydroxy-diphenyl)ether, 4,4'-dihydroxy-2,
6-dimethyldiphenyl ether, bis(4-hydroxy-3-isobutylphenyl) ether,
Bis(4-hydroxy-3-isopropylphenyl) ether, bis(4-hydroxy-3-chlorophenyl) ether, bis(4-hydroxy-
3-fluorophenyl) ether, bis(4-hydroxy-3-bromphenyl) ether, bis(4-hydroxynaphthyl) ether, bis(4-fluorophenyl) ether,
-hydroxy-3-chlornaphthyl) ether,
bis(2-hydroxybiphenyl) ether,
4,4'-dihydroxy-2,6-dimethoxydiphenyl ether, 4,4'-dihydroxy-2,5
-Di(hydroxyphenyl) ethers such as diethoxydiphenyl ether, and 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 divalent phenols has the general formula (where R ₃ is a methyl or ethyl group, R ₂ is an alkylidene group having 1 to 9 carbon atoms or other alkylene group, and p is 0 to 4), for example, 1,4-bis(4- hydroxybenzyl)benzene, 1,4-bis(4-hydroxybenzyl)tetramethylbenzene, 1,4-bis(4-hydroxybenzyl)tetraethylbenzene, 1,4-
Bis(p-hydroxycumyl)benzene, 1,3
-bis(p-hydroxycumyl)benzene and the like. Other polynuclear divalent phenols include, for example, initial condensates of phenols and carbonyl compounds (e.g., phenolic resin initial condensates, condensation reaction products of phenol and acrolein, condensation reaction products of phenol and glyoxal, phenol condensation reaction product of and pentanediallyl, condensation reaction product of resorcinol and acetone, xylene-
(phenol-formalin initial condensate), condensation products of phenols and polychloromethylated aromatic compounds (eg, condensation products of phenol and bischloromethylxylene), and the like. Further, the alkylene oxide to be subjected to the reaction with the divalent phenol is, for example, an alkylene oxide having 2 to 4 carbon atoms, and preferred examples include ethylene oxide, propylene oxide, butylene oxide, and mixtures thereof. . Thus, the alkylene oxide adduct of divalent phenol is produced by reacting the divalent phenol and alkylene oxide in the presence of an alkaline or acidic catalyst. The ratio of the divalent phenol to the alkylene oxide is preferably 1 to 10, preferably 1 to 3, per hydroxyl group of the divalent phenol. The alkylene oxide adduct of divalent phenol thus obtained is then subjected to a reaction with one selected from epihalogenohydrin, methyl epihalogenohydrin, and dihalogenohydrin in the presence of an alkali hydroxide catalyst. , to give a substituted or unsubstituted glycidyl ether compound. Here, examples of epihalogenohydrin, methyl epihalogenohydrin, and dihalogenohydrin include epichlorohydrin, epibromohydrin, methyl epichlorohydrin, methyl epibromohydrin, dichlorohydrin, and dibromohydrin, but especially epichlorohydrin,
Preferably, epibromohydrin or methylepichlorohydrin is used. Here, the reaction ratio of the alkylene oxide adduct of divalent phenol and one selected from epihalogenohydrin, methyl epihalogenohydrin, and dihalogenohydrin is 1 to 20 mol of the latter to 1 mol of the former. It is preferable that the epoxy equivalent of the substituted or unsubstituted glycidyl ether compound obtained is 200 to 600. Furthermore, the substituted or unsubstituted glycidyl ether compound is preferably heated at a temperature of 80 to 250°C in the presence of a catalyst to a temperature of 100°C.
By reacting dicarboxylic acids at ~180℃,
A high molecular weight epoxy resin is obtained. The epoxy equivalent of the high molecular weight epoxy resin obtained is preferably 1000 to 4000. Examples of the above dicarboxylic acids include maleic acid, adipic acid, succinic acid, phthalic acid, isophthalic acid, titetrahydrophthalic acid, and carboxyl group-terminated polyester compounds. Catalysts used in this reaction include inorganic alkalis such as caustic soda, caustic potash, and soda carbonate, triethylamine, triethanolamine,
Examples include tertiary amines such as dimethylamine and pyridine, imidazoles, quaternary ammonium salts such as tetramethylammonium chloride, Lewis acids such as boron trifluoride, aluminum chloride, tin tetrachloride, and titanium tetrachloride. . Further, the reaction ratio between the substituted or unsubstituted glycidyl etherified product and the dicarboxylic acid is arbitrarily determined so as to provide the epoxy equivalent weight required by the high molecular weight epoxy resin. Examples of the compound having a group reactive with a high molecular weight epoxy resin include a compound containing a phenol group, a compound containing an amino group, and a compound containing a carboxyl group. The compound containing a phenol group used at this time includes, for example, monovalent phenol or divalent phenol, but monovalent phenol is particularly preferred. Examples of such monovalent phenol include phenol, cresol, xylenol, t-
Examples include butylphenol. In addition, as a compound containing an amino group, for example, the first
Examples include primary amines and secondary amines, and particularly preferred is hydroxylamine containing a hydroxyl group. Examples of primary amines include methylamine, ethylamine, propylamine, etc.; examples of secondary amines include dibutylamine, etc.
Examples of hydroxylamine include ethanolamine, propanolamine, diethanolamine, and diisopropanolamine. Furthermore, as a compound having a carboxyl group,
For example, monocarboxylic acids or dicarboxylic acids may be mentioned, and monocarboxylic acids are preferred. Examples of monocarboxylic acids include acetic acid, propionic acid, and lactic acid; examples of dicarboxylic acids include maleic acid, adipic acid, succinic acid, phthalic acid, isophthalic acid, and tetrahydrophthalic acid. The reaction ratio between a high molecular weight epoxy resin and a compound having a group that is reactive with an epoxy group is such that the ratio of the group that is reactive with an epoxy group to the epoxy group that the former has is 1.1 to 1. 0.7,
In particular, a ratio of 1.0 to 0.9 is preferred. In addition, when the reaction between a high molecular weight epoxy resin and a compound having a group reactive with an epoxy group is used, for example, a compound having a phenol group or a carboxyl group is used as the compound having a group reactive with an epoxy group. It may be carried out at a temperature of, for example, 80 to 250°C in the presence of a catalyst such as
Can be carried out at a temperature of 150 °C. Compounds having more than one isocyanate group used in the present invention include, for example, toluene diisocyanate, xylylene diisocyanate,
Examples include crude diphenylmethane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate methyl ester, a 3-mole toluene diisocyanate adduct of trimethylolpropane, and high molecular weight polyisocyanates (prepolymers) obtained therefrom. The blending ratio of the compound having more than one isocyanate group is determined by the blending ratio of the hydroxyl group equivalent and isocyanate group equivalent in the polyether polyol resin.
A ratio of 0.4 to 1.2, preferably 0.7 to 1.0 is good. As the bituminous substance used in the composition of the present invention, coal tar, coal tar pitch, various types of cutback tar, swelling charcoal, asphalt, etc. can be used. There are various alternatives to bituminous substances, such as aromatic oil resins, coumaron resins, petroleum resins, and substances commonly used as diluents.
POP, DBP, and other high-boiling point neutral oils such as petroleum-based and coal-based oils can be used. The appropriate proportion of the bituminous substance and/or the substitute for the bituminous substance is 0.5 to 2 times the weight of the polyether polyol resin. In addition, various polyol compounds, curing catalysts, fillers, diluents, dehydrating agents, resins, etc. can be added to the composition of the present invention as necessary. Hereinafter, the present invention will be explained in more detail with reference to Examples.
Note that parts in the examples are based on weight. Production example of polyether polyol resin Production example 1 Add sodium hydroxide as a catalyst to 150 parts of a liquid epoxy resin (epoxy equivalent = 410) obtained by adding propylene oxide to bisphenol A and converting it into glycidyl ether and 30 parts of succinic acid at 180°C. The mixture was heated and stirred for 10 hours. The obtained high molecular weight epoxy resin had an epoxy equivalent weight of 1750. Furthermore, add 11 parts of phenol,
Polyol resin () was heated and stirred at 180℃ for 7 hours.
I got it. The polyol resin had a hydroxyl equivalent of 430, and was arbitrarily dissolved in an aromatic solvent such as xylene or toluene. Production Example 2 200 parts of a liquid epoxy resin (epoxy equivalent = 510) obtained by adding ethylene oxide to bisphenol A and converting it into glycidyl ether, 21 parts of adipic acid, and dimethylamine as a catalyst were added, and the mixture was heated and stirred at 160°C for 15 hours. The epoxy equivalent of the high molecular weight epoxy resin obtained was 1,900. Further, 22 parts of diethanolamine was added and stirred at 80°C for 3 hours to obtain a polyol resin (2). The hydroxyl equivalent of the polyol resin is 420, and xylene,
Optionally dissolved in an aromatic solvent such as toluene. Production Example 3 100 parts of a liquid epoxy resin (epoxy equivalent = 350) obtained by adding propylene oxide to bisphenol F and converting it into glycidyl ether, 45 parts of a polyester compound obtained from adipic acid and ethylene glycol (acid equivalent = 240), and water as a catalyst. Sodium oxide was added and the mixture was heated and stirred at 150°C for 10 hours. The obtained high molecular weight epoxy resin has an epoxy equivalent of 1500
It was hot. Furthermore, 12 parts of benzoic acid was added, and the mixture was stirred at 130°C for 7 hours. The obtained polyol resin (2) had a hydroxyl equivalent of 450 and was arbitrarily dissolved in an aromatic solvent such as xylene or toluene. Production Example 4 Diglycidyl ether obtained from bisphenol A and epichlorohydrin (epoxy equivalent =
190) Sodium hydroxide was added as a catalyst to 100 parts of succinic acid and 24 parts of succinic acid, and the mixture was heated and stirred at 150°C for 12 hours. The obtained high molecular weight epoxy resin had an epoxy equivalent weight of 970°C. Furthermore, add 12 parts of phenol,
Polyol resin () was heated and stirred at 170℃ for 6 hours.
I got it. The hydroxyl equivalent of the polyol resin is 270,
It does not dissolve with aromatic solvents such as xylene or toluene alone, so it is necessary to add a ketone solvent or alcohol solvent. Production Example 5 Diglycidyl ether obtained from bisphenol A and epichlorohydrin (epoxy equivalent =
450), 17 parts of adipic acid, and dimethylamine as a catalyst were added, and the mixture was heated and stirred at 150°C for 12 hours.
The epoxy equivalent of the obtained high molecular weight epoxy resin was 1,750. Furthermore, 10 parts of diethanolamine was added and stirred at 90°C for 2 hours to obtain a polyol resin (2). The hydroxyl equivalent of the polyol resin is 220, and xylene,
It does not dissolve in aromatic solvents such as toluene alone, so it is necessary to add ketone solvents and alcohol solvents. Production example 6 Epoxy resin obtained from bisphenol F and epichlorohydrin (epoxy equivalent = 350) 150
Sodium hydroxide was added as a catalyst to 62 parts of a polyester compound (acid equivalent = 240) obtained from adipic acid and ethylene glycol, and the mixture was heated and stirred at 150°C for 15 hours. The obtained high molecular weight epoxy resin had an epoxy equivalent weight of 1300. Furthermore, 21 parts of benzoic acid was added and the mixture was heated and stirred at 160°C for 7 hours to obtain a polyol resin (2). The hydroxyl equivalent of the polyol resin is 250, and it cannot be dissolved in an aromatic solvent such as xylene or toluene alone, so it is necessary to add a ketone solvent or an alcohol solvent. Examples 1 to 6, Comparative Examples 1 to 6 A mixture of polyol resin, solvent, bituminous material or its substitute, and filler (component A) and polyisocyanate (component B) in the proportions shown in Tables 1 and 2. The mixture was mixed and applied to a mild steel plate to a film thickness of 150 to 200 μm, and after curing at room temperature for 7 days, various tests were conducted. The results are shown in Tables 1 and 2.

【table】

【table】

【table】

【table】

Claims (1)

[Claims] 1 Polyether polyol resin obtained by reacting a high molecular weight epoxy resin obtained by reacting a substituted or unsubstituted glycidyl etherified product of an alkylene oxide adduct of divalent phenol with a dicarboxylic acid and a compound having a group reactive with an epoxy group. a compound having more than one isocyanate group per molecule; and a bituminous substance and/or its substitute.