JPS6351468B2 - - 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 divalent phenol 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 has one or more aromatic nuclei in the molecule, and the aromatic nucleus has 2
Refers to a substance in which 2 hydroxyl groups are substituted, and a mononuclear 2
phenols and polynuclear divalent 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 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 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 group, such as a sulfur or sulfoxide group. two or more alkylene or alkylidene groups separated by a bond containing polynuclear dihydric phenols. 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] or

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, a high molecular weight epoxy resin can be obtained by reacting the substituted or unsubstituted glycidyl etherified product with dihydric phenol at a temperature of 80 to 250°C in the presence of a catalyst. The epoxy equivalent of the high molecular weight epoxy resin obtained is preferably 1000 to 4000. Here, the above-mentioned divalent phenol may be any of the divalent phenols exemplified as the divalent phenols that can be used in the production of the alkylene oxide adduct of the above-mentioned divalent phenol. 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 dihydric phenol 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 the hydroxyamine 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.
DOP, 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. Incidentally, various curing catalysts, fillers, diluents, dehydrating agents, resins, etc. can be added to the composition of the present invention as required. Hereinafter, the present invention will be explained in more detail with reference to Examples.
Note that parts in the examples are based on weight. Examples 1 to 6 and Comparative Examples 1 to 6 (1) Production of polyether polyol resin Production example 1 150 parts of a liquid epoxy resin (epoxy equivalent = 410) obtained by adding propylene oxide to bisphenol A and converting it into glycidyl ether and bisphenol A. phenol
Add sodium hydroxide as a catalyst to 25 parts of A200
Heating and stirring was continued at ℃ for 10 hours. The obtained high molecular weight epoxy resin had an epoxy equivalent weight of 1250. Furthermore, 14 parts of phenol was added and heated and stirred at 200°C for 6 hours to form a polyether polyol resin ().
I got it. The polyether polyol resin had a hydroxyl equivalent of 420, and was arbitrarily dissolved in an aromatic solvent such as xylene or toluene. Production example 2 150 parts of liquid epoxy resin (epoxy equivalent = 510) obtained by adding ethylene oxide to bisphenol A and converting it into glycidyl ether, 17 parts of bisphenol sulfone, and dimethylamine as a catalyst were added.
Heating and stirring was continued at 180°C for 15 hours. The obtained high molecular weight epoxy resin had an epoxy equivalent weight of 1900. Furthermore, 10 parts of diethanolamine was added and stirred at 110°C for 3 hours to obtain a polyether polyol resin (2). The polyether polyol resin had a hydroxyl equivalent of 210, and was arbitrarily dissolved in an aromatic solvent such as xylene or toluene. Production example 3 150 parts of liquid epoxy resin (epoxy equivalent = 300) obtained by adding propylene oxide to bisphenol F and converting it into glycidyl ether and bisphenol
Add sodium hydroxide as a catalyst to 2 parts of F4 to 150
Heating and stirring was continued at ℃ for 18 hours. The obtained high molecular weight epoxy resin had an epoxy equivalent weight of 2,500.
Further, 10 parts of benzoic acid was added and the mixture was heated and stirred at 170°C for 7 hours to obtain a polyether polyol resin (2).
The hydroxyl equivalent of the polyether polyol resin is
340 and optionally dissolved in aromatic solvents such as xylene and toluene. Production Example 4 Sodium hydroxide was added as a catalyst to 150 parts of Asahi Denka Kogyo's Adeka Resin EP4100 (epoxy equivalent = 190) obtained from bisphenol A and epichlorohydrin and 65 parts of bisphenol A, and the mixture was heated and stirred at 180°C for 5 hours. The obtained high molecular weight epoxy resin had an epoxy equivalent weight of 975. Furthermore, 19 parts of phenol was added and the mixture was heated and stirred at 200°C for 6 hours to obtain a polyether polyol resin (2). The hydroxyl equivalent of the polyether polyol resin is 296,
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 5 150 parts of Asahi Denka Kogyo's Adekalezin EP5100 (epoxy equivalent = 450) obtained from bisphenol A and epichlorohydrin, 22 parts of bisphenol S, and dimethylamine as a catalyst were added, and the mixture was heated and stirred at 150°C for 8 hours. The obtained high molecular weight epoxy resin had an epoxy equivalent weight of 1100. Further, 17 parts of diethanolamine was added and stirred at 150°C for 2 hours to obtain a polyether polyol resin (2). The hydroxyl equivalent of the polyether polyol resin is 210, 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. Production Example 6 Sodium hydroxide was added as a catalyst to 150 parts of Asahi Denka Kogyo's Adekalezin EP4900 (epoxy equivalent = 187) obtained from bisphenol F and epichlorohydrin and 70 parts of bisphenol F, 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 2,300. Furthermore, 12 parts of benzoic acid was added and the mixture was heated and stirred at 170°C for 7 hours to obtain a polyether polyol resin (2). The hydroxyl equivalent of the polyether polyol resin is 280, 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. (2) Preparation and evaluation of coating resin composition A coating resin composition having the composition shown in Tables 1 and 2 was prepared using the polyether polyol resins [] to [] obtained in the above production examples. In order to evaluate their performance, the coating films were coated and dried for 7 days at room temperature, and then the physical properties of the coating films were tested. The results were as shown in Tables 1 and 2.

【table】

【table】

【table】

[Table] Examples 7 to 12, Comparative Examples 7 to 18 Polyether polyol resin (), (),
Coating resins having the compositions shown in Table 3 were prepared using () and (), and their compatibility was compared. The results were as shown in Table 3.

【table】

[Table] Comparative Examples 19-30 To 100 parts of epoxy resin EP5400 (manufactured by Asahi Denka Kogyo Co., Ltd., epoxy equivalent = 1000) obtained from bisphenol A and epichlorohydrin, 10 parts of diethanolamine was added and stirred at 110°C for 3 hours to form polyether. Polyol resin () (hydroxyl equivalent = 385)
I got it. Further, 5 parts of diethanolamine was added to 100 parts of EP5700 (manufactured by Asahi Denka Kogyo Co., Ltd., epoxy equivalent = 2000) and stirred at 110°C for 3 hours to obtain a polyether polyol resin (2) (hydroxyl equivalent = 735). The above polyether polyol resin (), ()
Coating resins having the compositions shown in Table 4 were prepared using the following methods, and their compatibility was compared. The results were as shown in Table 4.

【table】

[Table] Comparative Examples 31-34 Coating resins having the composition shown in Table 5 were prepared using polyether polyol resins (), () and polypropylene glycol (molecular weight = 1700), and the same as in Examples 1-6. Physical property tests were conducted. The results were as shown in Table 5.

【table】

【table】

Claims (1)

[Claims] 1 Substituted or unsubstituted glycidyl etherified product of alkylene oxide adduct of divalent phenol 2
a polyether polyol resin obtained by reacting a polyhydric phenol to obtain a high molecular weight epoxy resin, and further reacting this with a compound having a group reactive with an epoxy group, and a compound having more than one isocyanate group; A coating resin composition characterized by containing a bituminous substance and/or a substitute thereof.